Photochemistry and Pericyclic Reactions (PDFDrive) PDF
Photochemistry and Pericyclic Reactions (PDFDrive) PDF
Photochemistry and Pericyclic Reactions (PDFDrive) PDF
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COURSE GUIDE (CHM 414)
Introduction
The study of chemical reactions, isomerizations and physical behavior that may occur under
the influence of visible and/or ultraviolet light is called Photochemistry. The
Photochemistry course is concerned with the interaction of visible and ultraviolet light with
molecules, an important aspect of modern chemistry which is relevant to biology (e.g.
photosynthesis, vision), lasers, organic synthesis, reaction kinetics and atmospheric science
(e.g. the ozone hole). Some familiarity with concepts such as Hund’s rules, the Franck-
Condon principle, basic reaction kinetics and the steady-state approximation is expected. On
the other hand, pericyclic reactions represent an important class of concerted (single step)
processes involving π-systems. It is a chemical reaction in which concerted reorganization of
bonding takes place throughout a cyclic array of continuously bonded atoms. The term
embraces a variety of processes, including cycloadditions, cheletropic reactions, electrocyclic
reactions and sigmatropic rearrangements (provided they are concerted).
Course Description
In this course (CHM 414) titled “photochemistry and pericyclic reaction”, you will be
presented information in a structured way to make leaning easier. This course exposes
students to the fundamental principles that are foundational to understanding photochemical
transformations. Each unit is planned in an easy to follow pattern for beginners in this aspect
of chemistry. We have adopted a step-by-step approach in order to introduce you to a
fascinating world of excited-state reactions and concerted reactions involving a cyclic flow of
electrons through a single transition state. All the units follow the same pattern and so after
the first unit the rest will become easy to follow.
Course Aims
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This course aims at providing you the necessary background on the basics of photochemistry
so as to enable you understand the underlying mechanism for all photochemical processes. It
also intends to enhance a detailed understanding of the concept of the processes of
pericyclic reactions and the stereochemical outcomes of these highly stereospecific reactions.
Course Objectives
In order to be able to successfully complete this course, you are required to carefully study
each unit along with recommended textbooks and other materials that may be provided by the
National Open University. You may also need to exploit other e-reading such as internet for
further useful information on the course. Each unit contains self assessment exercise and at
certain points in the course you would be required to submit assignment for grading and
recording purposes. You are also to participate in the final examination at the end of the
course. It is recommended that you devote an abundant time to reading and comprehension. It
is highly necessary that you avail yourself the opportunity of attending the tutorial sessions
where you will be able to compare your understanding of the course contents with your
colleagues.
Course Materials
1. A course guide which spells out the details of photochemistry and pericyclic reactions
including the aims and objectives.
2. The study units (presented in two modules) with detailed learning information. Each study
unit has a set of performance objectives along with other relevant learner guide.
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Study Units
Module One
Unit 1- The electromagnetic spectrum: This Unit gives the range of all possible frequencies
of electromagnetic radiation and the "electromagnetic spectrum" of an object as the
characteristic distribution of electromagnetic radiation emitted or absorbed by that object.
Unit 3 – Light absorption and fate of the excited state: Reveals what happens to molecules
when they absorb light, the variety of processes and different mechanistic pathways they
undergo.
Unit 4 – Selection rules and photophysical parameters: Looks at the way absorbed or
generated photons are analyzed to predict the likelihood that a physical system will change
from one state to another or will be unable to make such a transition.
Unit 5 –Lasers: In this Unit the properties of Laser and the wide variety of applications in all
walks of life to which Laser has been engaged were discussed.
MODULE TWO
Unit 2 - Types of pericyclic reactions: Explains the major categories of pericyclic reactions
and compares different types.
Unit 3 - Analysis of pericyclic reactions: This Unit applies orbital correlation diagram
method and the frontier molecular orbital (FMO) approach to analyze pericyclic reactions.
The individual units of this book are organized according to the following format: unit title,
introduction to the unit, unit learning objectives and text, summary, tutor-marked assignments
(TMA) and suggested references for further reading. We chose this format in order to aid the
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reader in comprehending the material and to stimulate him to probe the unit topics further.
The TMAs are meant to test your basic understanding and comprehension of the course
materials, which is a prerequisite for achieving the stated aims and objectives of the course.
Assessment
The course assessment consists of three aspects namely the self assessment exercise, the tutor
marked assignment and the written examination/end of course examination. It is essential that
you attempt all exercises and assignments and submit appropriately to the course facilitator
for grading. Let your answers be concise and as accurate as possible. You are expected to
consult other materials in addition to your course materials in order to be able to present
accurate answers to the questions. Kindly note that the tutor marked assignment covers only
30% of the total marks for the course.
The TMA is a continuous assessment component of your course. It accounts for 30% of the
total score. You will be given a number of TMAs to answer. Nearly all of them must be
answered before you are allowed to sit for the end of the course examination. The TMAs will
be given to you by your facilitator and returned after you have done the assignment. Note that
these assignments are already contained in the assignment file to be given to you. You may
do yourself good by reading and researching well before you attempt to answer the questions.
There are few hours of tutorials provided in support of this course. You will be informed
appropriately of the name, telephone number and e-mail address of your facilitator. In
addition, the time, dates and location of the tutorial lessons will be communicated
beforehand. You are required to mail or submit your Tutor Marked Assignment to your
facilitator, at least two working days, before the schedule date. Note that all the submitted
assignments will be duly marked by the facilitator with further comments that can improve on
your performances. The facilitator will from time to time take track record of your
comprehension, progress and difficulty in the course. Be kind enough to attend tutorial
lessons at the fixed appointment. It is probably the only avenue to meet face to face and
discuss with you facilitator. There, you will be able to ask questions or seek clarification on
seemingly grey areas in the course material. You may as well have prepared questions and
comments for your facilitator before the due date. An active participation during the tutorial
lessons will be an added advantage to boost your confidence level. In case any of the
situations listed below arises, do not hesitate to intimate your facilitator using his or her
telephone number or via e-mail address;
You do not understand any part of the study or the assigned readings
You are not skill enough to attempt the self assessment exercise
The questions in the TMAs are not clearly understood
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Textbooks
There are numerous books and other materials that treat Structure and Bonding; some of
these are listed at the end of units. In addition, the internet provides a lot of information
relating to the course title; the learner is encouraged to use the internet, though with some
level of caution. The learner may wish to consult any of the following resources in aid of
effective learning:
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TABLE OF CONTENTS
Pag
e
MODULE ONE
1.0 INTRODUCTION 1
2.0 OBJECTIVES 1
3.3.2 Microwaves 4
3.3.6 X-rays 6
4.0 SUMMARY 9
6.0 REFERENCES 10
1.0 INTRODUCTION 11
2.0 OBJECTIVES 11
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3.0 MAIN CONTENT 11
3.3 Photochemistry 13
3.4.1 Dissociation 15
3.4.2 Energy transfer 15
3.4.3 Luminescence 15
3.5 Applications of photochemistry 16
3.6 Experimental set-up 16
3.6.1 Excitation 17
1.0 INTRODUCTION 19
2.0 OBJECTIVES 19
4.0 SUMMARY 30
6.0 REFERENCES 30
1.0 INTRODUCTION 31
2.0 OBJECTIVES 31
3.1Selection rules 31
3.1.1 Spin selection rule (∆S = 0) 32
3.1.2 LaPorte selection rule (g↔u; ∆l = ±1) 32
3.1.3 Franck-Condon Selection Rule 32
3.1.4 Orbital Overlap Selection Rule 32
3.2 The Quantum Yield 33
3.2.1 Calculating the Number of Photons Absorbed 34
3.3 The excited state lifetime 36
3.3.1Exponential Decay of the Excited State 38
3.4 Rate Constants for Excited State Deactivation 39
3.5 Fluorescence quenching 41
4.0 SUMMARY 43
5.0 TUTOR-MARKED ASSIGNMENT 43
6.0 REFERENCES 44
UNIT 5 – LASERS 45
1.0 INTRODUCTION 45
2.0 OBJECTIVES 45
3.1.1 Monochromaticity 46
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3.1.2 Directionality 47
3.1.3 Coherence 49
3.3.1 Amplification 55
4.0 SUMMARY 58
5.0 TUTOR-MARKED ASSIGNMENT 59
6.0 REFERENCES 59
UNIT 6 – PHOTOCHEMICAL REACTIONS 60
1.0 INTRODUCTION 60
2.0 OBJECTIVES 60
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3.3.2 Cycloaddition of unsaturated molecules 65
3.3.3 Photofragmentation 65
3.3.4 Photooxidation 66
3.3.5 Photohydration 66
3.3.7 Photorearrangement 68
4.0 SUMMARY 70
5.0 TUTOR-MARKED ASSIGNMENTS 71
6.0 REFERENCES 71
MODULE TWO
1.0 INTRODUCTION 72
2.0 OBJECTIVES 73
4.0 SUMMARY 77
5.0 TUTOR-MARKED ASSIGNMENTS 77
6.0 REFERENCES 77
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UNIT 2 - TYPES OF PERICYCLIC REACTIONS 78
1.0 INTRODUCTION 78
2.0 OBJECTIVES 78
4.0 SUMMARY 88
5.0 TUTOR-MARKED ASSIGNMENTS 88
6.0 REFERENCES 88
2.0 OBJECTIVES 89
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4.0 SUMMARY 105
5.0 TUTOR-MARKED ASSIGNMENTS 106
6.0 REFERENCES 106
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UNIT 1 – THE ELECTROMAGNETIC SPECTRUM
1.0. INTRODUCTION
2.0. OBJECTIVES
After studying this Unit, you should be able to:
• Describe and electromagnetic wave and its properties.
• Describe properties of light in relation to particles and to electromagnetic
waves.
• Describe the two components of an electromagnetic radiation
• State the range (various divisions) of the electromagnetic spectrum
• Explain the wave-particle duality of light
• Carry out simple calculations using the parameters of light (wavelength,
frequency, velocity, wave number and energy)
• State the physical processes that could take place when electromagnetic
radiation interacts with matter
where:
• c = 299,792,458 m s-1 is the speed of light in vacuum
• h = 6.62606896(33)×10−34 J s = 4.13566733(10)×10−15 eV s is Planck's constant.
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Whenever electromagnetic waves exist in a medium with matter, their wavelength is
decreased. Wavelengths of electromagnetic radiation, no matter what medium they are
travelling through, are usually quoted in terms of the vacuum wavelength, although this is not
always explicitly stated.
Generally, electromagnetic radiation is classified by wavelength into radio wave, microwave,
terahertz (or sub-millimeter) radiation, infrared, the visible region we perceive as light,
ultraviolet, X-rays and gamma rays. The behaviour of EM radiation depends on its
wavelength. When EM radiation interacts with single atoms and molecules, its behaviour also
depends on the amount of energy per quantum (photon) it carries.
Spectroscopy can detect a much wider region of the EM spectrum than the visible range of
400 nm to 700 nm. A common laboratory spectroscope can detect wavelengths from 2 nm to
2500 nm. Detailed information about the physical properties of objects, gases, or even stars
can be obtained from this type of device. Spectroscopes are widely used in astrophysics. For
example, many hydrogen atoms emit a radio wave photon that has a wavelength of 21.12 cm.
Also, frequencies of 30 Hz and below can be produced by and are important in the study of
certain stellar nebulae and frequencies as high as 2.9×1027 Hz have been detected from
astrophysical sources.
Region of the
Main interactions with matter
spectrum
Collective oscillation of charge carriers in bulk material (plasma
Radio oscillation). An example would be the oscillation of the electrons in an
antenna.
Microwave
through far Plasma oscillation, molecular rotation
infrared
Near infrared Molecular vibration, plasma oscillation (in metals only)
Molecular electron excitation (including pigment molecules found in
Visible
the human retina), plasma oscillations (in metals only)
Excitation of molecular and atomic valence electrons, including ejection
Ultraviolet
of the electrons (photoelectric effect)
Excitation and ejection of core atomic electrons, Compton scattering
X-rays
(for low atomic numbers)
Energetic ejection of core electrons in heavy elements, Compton
Gamma rays scattering (for all atomic numbers), excitation of atomic nuclei,
including dissociation of nuclei
Creation of particle-antiparticle pairs. At very high energies a single
High-energy
photon can create a shower of high-energy particles and antiparticles
gamma rays
upon interaction with matter.
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3.3. Types of radiation
The types of electromagnetic radiation are broadly classified into the following classes:
1. Gamma radiation
2. X-ray radiation
3. Ultraviolet radiation
4. Visible radiation
5. Infrared radiation
6. Microwave radiation
7. Radio waves
This classification goes in the increasing order of wavelength, which is characteristic of the
type of radiation. While, in general, the classification scheme is accurate, in reality there is
often some overlap between neighboring types of electromagnetic energy. For example, SLF
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radio waves at 60 Hz may be received and studied by astronomers, or may be ducted along
wires as electric power, although the latter is, in the strict sense, not electromagnetic radiation
at all (see near and far field) The distinction between X-rays and gamma rays is based on
sources: gamma rays are the photons generated from nuclear decay or other nuclear and
subnuclear/particle process, whereas X-rays are generated by electronic transitions involving
highly energetic inner atomic electrons. In general, nuclear transitions are much more
energetic than electronic transitions, so gamma-rays are more energetic than X-rays, but
exceptions exist. By analogy to electronic transitions, muonic atom transitions are also said to
produce X-rays, even though their energy may exceed 6 megaelectronvolts (0.96 pJ), whereas
there are many (77 known to be less than 10 keV (1.6 fJ)) low-energy nuclear transitions
(e.g., the 7.6 eV (1.22 aJ) nuclear transition of thorium-229), and, despite being one million-
fold less energetic than some muonic X-rays, the emitted photons are still called gamma rays
due to their nuclear origin.
Also, the region of the spectrum of the particular electromagnetic radiation is reference
frame-dependent (on account of the Doppler shift for light), so EM radiation that one
observer would say is in one region of the spectrum could appear to an observer moving at a
substantial fraction of the speed of light with respect to the first to be in another part of the
spectrum. For example, consider the cosmic microwave background. It was produced, when
matter and radiation decoupled, by the de-excitation of hydrogen atoms to the ground state.
These photons were from Lyman series transitions, putting them in the ultraviolet (UV) part
of the electromagnetic spectrum. Now this radiation has undergone enough cosmological red
shift to put it into the microwave region of the spectrum for observers moving slowly
(compared to the speed of light) with respect to the cosmos. However, for particles moving
near the speed of light, this radiation will be blue-shifted in their rest frame. The highest-
energy cosmic ray protons are moving such that, in their rest frame, this radiation is
blueshifted to high-energy gamma rays, which interact with the proton to produce bound
quark-antiquark pairs (pions).
3.3.2. Microwaves
The super-high frequency (SHF) and extremely high frequency (EHF) of microwaves come
after radio waves. Microwaves are waves that are typically short enough to employ tubular
metal waveguides of reasonable diameter. Microwave energy is produced with klystron and
magnetron tubes, and with solid state diodes such as Gunn and IMPATT devices.
Microwaves are absorbed by molecules that have a dipole moment in liquids. In a microwave
oven, this effect is used to heat food. Low-intensity microwave radiation is used in Wi-Fi,
although this is at intensity levels unable to cause thermal heating.
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Volumetric heating, as used by microwave ovens, transfers energy through the material
electromagnetically, not as a thermal heat flux. The benefit of this is a more uniform heating
and reduced heating time; microwaves can heat material in less than 1% of the time of
conventional heating methods.
When active, the average microwave oven is powerful enough to cause interference at close
range with poorly shielded electromagnetic fields such as those found in mobile medical
devices and cheap consumer electronics.
1. Far-infrared, from 300 GHz (1 mm) to 30 THz (10 µm). The lower part of this range
may also be called microwaves. This radiation is typically absorbed by so-called
rotational modes in gas-phase molecules, by molecular motions in liquids, and by
phonons in solids. The water in Earth's atmosphere absorbs so strongly in this range
that it renders the atmosphere in effect opaque. However, there are certain wavelength
ranges ("windows") within the opaque range that allow partial transmission, and can
be used for astronomy. The wavelength range from approximately 200 µm up to a few
mm is often referred to as "sub-millimeter" in astronomy, reserving far infrared for
wavelengths below 200 µm.
2. Mid-infrared, from 30 to 120 THz (10 to 2.5 µm). Hot objects (black-body radiators)
can radiate strongly in this range. It is absorbed by molecular vibrations, where the
different atoms in a molecule vibrate around their equilibrium positions. This range is
sometimes called the fingerprint region, since the mid-infrared absorption spectrum
of a compound is very specific for that compound.
3. Near-infrared, from 120 to 400 THz (2,500 to 750 nm). Physical processes that are
relevant for this range are similar to those for visible light.
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different shades and hues, and through this insufficiently-understood psychophysical
phenomenon, most people perceive a bowl of fruit.
At most wavelengths, however, the information carried by electromagnetic radiation is not
directly detected by human senses. Natural sources produce EM radiation across the
spectrum, and our technology can also manipulate a broad range of wavelengths. Optical
fibre transmits light that, although not necessarily in the visible part of the spectrum, can
carry information. The modulation is similar to that used with radio waves.
3.3.6. X-rays
After UV come X-rays, which, like the upper ranges of UV are also ionizing. However, due
to their higher energies, X-rays can also interact with matter by means of the Compton effect.
Hard X-rays have shorter wavelengths than soft X-rays. As they can pass through most
substances, X-rays can be used to 'see through' objects, the most notable use being diagnostic
X-ray images in medicine (a process known as radiography), as well as for high-energy
physics and astronomy. Neutron stars and accretion disks around black holes emit X-rays,
which enable us to study them. X-rays are given off by stars and are strongly emitted by some
types of nebulae.
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Note that there are no precisely defined boundaries between the bands of the electromagnetic
spectrum. Radiations of some types have a mixture of the properties of those in two regions
of the spectrum. For example, red light resembles infrared radiation in that it can resonate
some chemical bonds.
The electromagnetic radiations are produced by the vibrations of a charged particle. The
properties of light can be explained by considering it as either wave or particle as follows.
Wavelength (λ): The distance between two successive similar points on a wave is called as
wavelength. It is denoted by λ.
Units: cm, Angstroms (Ao), nano meters (nm), milli microns (mµ) etc.,
Note:
1 Ao = 10-8 cm.
1 nm= 10-9m = 10-7cm
Frequency (ν): The number of vibrations done by a particle in unit time is called frequency.
It is denoted by 'ν'.
Units: cycles per second = Hertz = sec-1.
Velocity (c): Velocity is defined as the distance covered by the wave in unit time. It is
denoted by 'c'.
Velocity of light = c = 3.0 x 108 m.sec-1 = 3.0 x 1010 cm.sec-1
Note: For all types of electromagnetic radiations, the velocity is a constant value. The relation
between velocity (c), wavelength (λ) and frequency (ν) can be given by following equation:
velocity = frequency x wavelength (c = νλ).
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Wave number( ): The number of waves spread in a length of one centimeter is called wave
number. It is denoted by . It is the reciprocal of wavelength, λ.
Amplitude: The distance from the midline to the peak or the trough is called amplitude of the
wave. It is usually denoted by 'A' (a variable). Amplitude is a measure of the intensity or
brightness of light radiation.
Following are the conclusions that can be drawn from above graphs.
1) At a given temperature, the intensity of radiation increases with wavelength and reaches a
maximum value and then starts decreasing.
2) With increase in temperature, the wavelength of maximum intensity (λmax) shifts towards
lower wavelengths. According to classical physics, energy should be emitted continuously
and the intensity should increase with increase in temperature. The curves should be as
shown by dotted line.
In order to explain above experimental observations Max Planck proposed the following
theory.
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Quantum theory:
1) Energy is emitted due to vibrations of charged particles in the black body.
2) The radiation of energy is emitted or absorbed discontinuously in the form of small
discrete energy packets called quanta.
3) Each quantum is associated with definite amount of energy which is given by the equation
E = hν
Where h = planck's constant = 6.625 x 10-34 J. sec = 6.625 x10-27 erg. sec
ν = frequency of radiation
4) The total energy of radiation is quantized i.e., the total energy is an integral multiple of hν.
It can only have the values of 1 hν or 2 hν or 3 hν. It cannot be the fractional multiple of hν.
5) Energy is emitted and absorbed in the form of quanta but propagated in the form of
waves.
The following table gives approximate wavelengths, frequencies, and energies for
selected regions of the electromagnetic spectrum:
Visible 7000 - 4000 7 x 10-5 - 4 x 10-5 4.3 x 1014 - 7.5 x 1014 2-3
Gamma Rays < 0.1 < 10-9 > 3 x 1019 > 105
The notation "eV" stands for electron-volts, a common unit of energy measure in atomic
physics.
4.0. SUMMARY
The electromagnetic (EM) spectrum is just a name that scientists give a bunch of types
of radiation when they want to talk about them as a group. Radiation is energy that
travels and spreads out as it goes-- visible light that comes from a lamp in your house
and radio waves that come from a radio station are two types of electromagnetic
radiation. Other examples of EM radiation are microwaves, infrared and ultraviolet
light, X-rays and gamma-rays. Hotter, more energetic objects and events create higher
energy radiation than cool objects. Only extremely hot objects or particles moving at
very high velocities can create high-energy radiation like X-rays and gamma-rays.
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5.0. TUTOR-MARKED ASSIGNMENT
1. What are the different types of electromagnetic radiation? What kind of
electromagnetic radiation has the shortest wavelength? The longest?
2. List any three physical processes that take place when radiant energy interacts
with an object
3. Calculate the wavelength of the electromagnetic radiation whose frequency is
7500 x1012 Hz?
4. Calculate the frequency of radiation with a wavelength of 442 nm.
5. Calculate the frequency of radiation with a wavelength of 4.55 x 10-9 cm.
6. A certain source emits radiation of wavelength 500.0 nm. What is the energy,
in kJ, of one mole of photons of this radiation?
7. Determine the wavelength (in meters) of photons with the following
energies:
a) 92.0 kJ/mol
b) 8.258 x 10-4 kJ/mol
c) 1870 kJ/mol
6.0. REFERENCES
1.1. en.wikipedia.org/wiki/Electromagnetic_spectrum
1.2. http://www.adichemistry.com/general/atomicstructure/quantumtheory/quantu
m-theory.html
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UNIT 2 – INTRODUCTION TO PHOTOCHEMISTRY
1.0. INTRODUCTION
Today photochemistry has become one of the most powerful research tools. Compounds of
different molecules are occurred through various photochemical reactions like CO2, NH3 and
methane. Other examples of photochemical reactions are formation of O3, smog, Vitamin D
and many more. A new field in photochemistry called photobiology helps us to understand
the mechanism of photosynthesis (process by which plants make their own food by the
absorption of sunlight).
Also photochemistry helps us to form some typical compounds like Vitamin D, cubanes, and
several cleaning agents which all are made by various chemical reactions of photochemistry.
The formation of laser light is only possible through photochemistry. LASER stands for Light
Amplification by Stimulated Emission of Radiations. LASER contain monochromatic rays
with coherent radiations, these rays can be easily focused to a small point. Due to this
property, LASER light is used for cutting hard material like metal, diamond etc, also there is
some application of LASER light in medical field.
Photochemical reactions occur all around us, being an important feature of many of the
chemical processes occurring in living systems and in the environment. The power and
versatility of photochemistry is becoming increasingly important in improving the quality of
our lives, through health care, energy production and the search for ‘green’ solutions
twosome of the problems of the modern world. Many industrial and technological processes
rely on applications of photochemistry, and the development of many new devices has been
made possible by spin-off from photochemical research.
Photochemistry is the study of the chemical reactions and physical changes that result from
interactions between matter and visible or ultraviolet light.
The principal aim of this Unit is to familiarise the reader with basic ideas relating to light and
matter and the interaction between them.
2.0. OBJECTIVES
After studying this Unit, you should be able to:
• Explain the importance of the electromagnetic radiation in understanding the
nature of matter
• Distinguish between thermal and photochemical reactions
• State the classical laws of photochemistry
• Explain the importance of UV-Visible radiation in photochemistry
• Discuss the applications of photochemistry
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3.1.1. Absorption of Light by Atoms and Molecules
The basic ideas:
Light consists of oscillating electric and magnetic fields.
Because nuclei and electrons are charged particles, their motions in atoms and molecules
generate oscillating electric fields.
An atom or molecule can absorb energy from light if the frequency of the light oscillation and
the frequency of the electron or molecular "transition motion" match. Unless these
frequencies match, light absorption cannot occur. The "transition motion" frequency is
related to the frequencies of motion in the higher and lower energy states by the equation:
∆E = E 2 − E1 = hν
By measuring the frequencies of light absorbed by an atom or molecule, one can determine
the frequencies of the various transition motions that the atom or molecule can have. Thus
light absorption can be used to probe the dynamics of atoms and molecules.
These ideas are the basis for the techniques of spectroscopy, which is the study of the
interaction of light and matter. The word means "measurement of spectrum," where the
spectrum of a substance is the array of frequencies of light absorbed by its atoms or
molecules.
Many chemical reactions occur only when a molecule is provided the necessary “activation
energy”. A simple example can be the combustion of gasoline (a hydrocarbon) into carbon
dioxide and water. In this reaction, the activation energy is provided in the form of heat or a
spark. In case of photochemical reactions light provides the activation energy. Simplistically,
light is one mechanism for providing the activation energy required for many reactions. If
laser light is employed, it is possible to selectively excite a molecule so as to produce a
desired electronic and vibrational state. Equally, the emission from a particular state may be
selectively monitored, providing a measure of the population of that state. If the chemical
system is at low pressure, this enables scientists to observe the energy distribution of the
products of a chemical reaction before the differences in energy have been smeared out and
averaged by repeated collisions.
The absorption of a photon of light by a reactant molecule may also permit a reaction to
occur not just by bringing the molecule to the necessary activation energy, but also by
changing the symmetry of the molecule’s electronic configuration, enabling an otherwise
inaccessible reaction path, as described by the Woodward-Hoffmann selection rules. A 2+2
cycloaddition reaction is one example of a pericyclic reaction that can be analyzed using
these rules or by the related frontier molecular orbital theory.
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Table 1.1 Difference between thermal and photochemical reactions
3.3. Photochemistry
Photochemistry is the study of how two of the most fundamental components of the universe,
light and matter, interact with each other. The field of photochemistry can be classified in
terms of photophysics (interaction of light with molecules which results in net physical, not
chemical, changes) and photochemistry (interaction of light with molecules which results in
net chemical changes).
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mole to nearly 1000 kJ mol-1, depending on the bond. Visible light, having wavelengths
ranging from 400-700 nanometers, corresponds to energies ranging from approximately 300-
170 kJ mol-1, respectively. Note that this is enough energy to dissociate relatively weak bonds
such as the single oxygen (O-O) bond in hydrogen peroxide (HOOH), which is why
hydrogen peroxide must be stored in a light-proof bottle.
Ultraviolet light, having wavelengths ranging from 200-400 nm, corresponds to higher
energies ranging from approximately 600-300 kJ mol-1, respectively. Ultraviolet light can
dissociate relatively strong bonds such as the double oxygen (O=O) bond in molecular
oxygen (O2) and the double C=O bond in carbon dioxide (CO2); ultraviolet light can also
remove chlorine atoms from compounds such as chloromethane (CH3Cl). The ability of
ultraviolet light to dissociate these molecules is an important aspect of the stability—and
destruction—of ozone molecules in the upper atmosphere.
Followed by:
i) AB* → A + B Dissociation
+ –
ii) AB* → AB + e Ionization
iii) AB* → BA Isomerization
iv) AB* + C → AC + B or ABC Reaction
v) AB* + DE → AB + DE* Energy Transfer (intermolecular)
vi) AB* + M → AB + M Physical Quenching
vii) AB* → AB Energy Transfer (intramolecular)
viii) AB* → AB + hν Luminsecence
3.4.1. Dissociation
The energy of an absorbed photon may be sufficient to break molecular bonds (path i),
creating two or more atomic or molecular fragments. An important example of
photodissociation is found in the photochemistry of stratospheric ozone. Ozone (O3) is
produced in the stratosphere from molecular oxygen (O2) through the following pair of
reactions: O2 + hν → O + O and O + O2 → O3 where hν represents the energy of a photon of
ultraviolet light with a wavelength less than 260 nm. Ozone is also dissociated by short-
wavelength ultraviolet light (200-300 nm) through the reaction: O3 + hν → O2 + O. The
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oxygen atom formed from this reaction may recombine with molecular oxygen to regenerate
ozone, thereby completing the ozone cycle. The great importance of stratospheric ozone is
that it absorbs harmful short-wavelength ultraviolet light before it reaches the Earth's surface,
thus serving as a protective shield.
An electronically excited species may react with a second species to produce a new product,
or set of products (path iv). For example, the products of the ultraviolet dissociation of ozone
(reaction 5) are themselves electronically excited: O3 + hν → O * 2 + O*. These excited
fragments may react with other atmospheric molecules such as water: O* + H2O → OH +
OH. Or they may react with ozone: O * 2 + O3 → 2O2 + O. These reactions do not readily
occur for the corresponding non-excited species, confirming the importance of electronic
excitation in determining reactivity.
3.4.3. Luminescence
Although it is not strictly a photochemical reaction, another pathway by which the excited
species may reduce its energy is by emitting a photon of light. This process is called
luminescence (path viii). Luminescence includes the processes of fluorescence (prompt
emission of a photon) and phosphorescence (delayed emission of a photon). Optical
brighteners in laundry detergents contain substances that absorb light of one wavelength,
usually in the ultraviolet range, but emit light at a longer wavelength, usually in the visible
range—thereby appearing to reflect extra visible light and making clothing appear whiter.
This process is called fluorescence and only occurs while the substance is being illuminated.
The related process, phosphorescence, persists after the excitation source has been removed
and is used in "glow-in-the-dark" items.
28
3.5. Applications of Photochemistry
Many important processes involve photochemistry. The premier example is photosynthesis,
in which most plants use solar energy to convert carbon dioxide and water into glucose,
disposing of oxygen as a side-product. Humans rely on photochemistry for the formation of
vitamin D. In fireflies, an enzyme in the abdomen catalyzes a reaction that results in
bioluminescence.
Photochemistry can also be highly destructive. Medicine bottles are often made with
darkened glass to prevent the drugs from photodegradation. A pervasive reaction is the
generation of singlet oxygen by photosensitized reactions of triplet oxygen. Typical
photosensitizers include tetraphenylporphyrin and methylene blue. The resulting singlet
oxygen is an aggressive oxidant, capable of converting C-H bonds into C-OH groups. In
photodynamic therapy, light is used to destroy tumors by the action of singlet oxygen.
Many polymerizations are started by photoinitiatiors, which decompose upon absorbing light
to produce the free radicals for Radical polymerization.
29
3.6.1. Excitation
Photoexcitation is the first step in a photochemical process where the reactant is elevated to a
state of higher energy, an excited state. The photon can be absorbed directly by the reactant
or by a photosensitizer, which absorbs the photon and transfers the energy to the reactant.
The opposite process is called quenching when a photoexited state is deactivated by a
chemical reagent.
Most photochemical transformations occur through a series of simple steps known as primary
photochemical processes. One common example of these processes is the excited state proton
transfer (ESPT).
In an industrial application, about 100,000 tonnes of benzyl chloride are prepared annually by
the gas-phase photochemical reaction of toluene with chlorine. The light is absorbed by
chlorine molecule, the low energy of this transition being indicted by the yellowish color of
the gas. The photon induces homolysis of the Cl-Cl bond, and the resulting chlorine radical
converts toluene to the benzyl radical:
Cl2 + hν → 2 Cl·
C6H5CH3 + Cl· → C6H5CH2· + HCl
C6H5CH2· + Cl· → C6H5CH2Cl
30
In a related reaction, photolysis of iron pentacarbonyl affords diiron nonacarbonyl (see
figure):
2 Fe(CO)5 → Fe2(CO)9 + CO
4.0. SUMMARY
• The concept of photochemistry is introduced and explained.
• Interaction of radiation with matter is discussed and difference between thermal and
photochemical processes highlighted.
• Laws of photochemistry: Grothus-Draper law and Stark-Einstein law provide basis
for understanding photochemical transformations.
• Examples of photochemical organic reactions are electrocyclic reactions and
photoisomerization
• The photoactivity of coordination and inorganic compounds is highlighted
• Many important processes involve photochemistry. The premier example is
photosynthesis, in which most plants use solar energy to convert carbon dioxide
and water into glucose, disposing of oxygen as a side-product.
6.0. REFERENCES
1. http://en.wikipedia.org/wiki/Photochemistry
2. http://science.jrank.org/pages/5157/Photochemistry
31
UNIT 3 – LIGHT ABSORPTION AND FATE OF THE EXCITED STATE
1.0. INTRODUCTION
Photochemistry is the study of what happens to molecules when they absorb light. Therefore
it is important to consider the factors affecting whether and how efficiently molecules absorb.
In addition, in the very short time-frame after a molecule has absorbed light, it can undergo a
variety of processes. In applications, we may desire a particular process, so again an
understanding of what pathways are available to excited states is important so that systems
can be optimised as required (e.g. by changing solvent, modifying the molecule).
Electronic excited states are thermodynamically unstable. They persist for lifetimes that are
normally about 10 nanoseconds for many medium sized organic molecules. A number of
transition metal complexes have lifetimes of about 1 microsecond. Triplet states, resulting
from a spin inter-conversion process in the excited state, have quite long lifetimes, sometimes
to beyond 1 millisecond.
Closed shell organic species that are electrically neutral always have single electronic ground
states; electronic selection rules require that absorption of light can occur only when the
electronic spin multiplicity is unchanged during the transition. However, molecular vibrations
and interactions between neighbouring molecules provide mechanisms for molecules to jump
between electronic energy levels either with the same or different spin multiplicity.
As molecules relax from excited states, they can proceed along many different mechanistic
pathways. A simple fate of an excited state molecule is to emit fluorescence. Fluorescence is
the light emission that occurs from the v' = 0 excited electronic state back down to the ground
electronic state. Spontaneous emission is the normal fluorescence that occurs with a random
probability. Stimulated emission is the reverse of a (stimulated) absorption transition, where
a photon of precisely the correct wavelength and direction comes along and knocks the
excited state down to the ground state, taking with it a second identical photon. LASERs
(Light Amplification by Stimulated Emission of Radiation) function when an excited state
reaches a population inversion, and all of the photons emitted from the gain medium have the
same characteristics. Lasers misbehave, or cease to function when stimulated emission starts
to lose the rate competition against spontaneous emission.
2.0. OBJECTIVES
After studying this Unit, you should be able to:
• Describe the process of light absorption by an atom or molecule
• Describe the fate of an electronically excited molecule
• Explain the impact of electromagnetic radiation on atomic and molecular
structure
• State and explain the Franck-Condon Principle
• List the important photophysical processes
• Draw the Jablonski diagram and use it to explain the fate of an electronically
excited molecule
• Discuss the relationship between the Franck-Condon principle and the Stokes’
shift
32
3.0. MAIN CONTENT
Figure 1: Regions of the electromagnetic spectrum and their impact on atom structure
Figure 2: Absorption of a photon of visible light causes a d-d transition in Ru(II) giving the
molecule a visible colour.
33
3.1.1. Excited electronic states carry vibrational and rotational
excitation immediately after their creation.
Though absorption of light most often occurs from ground electronic states for which the
vibrational quantum number is v = 0, the rotational quantum number J is zero only for
very cold, isolated molecules (such as those prepared in a gas-phase supersonic free jet
expansion, or kept in a liquid helium cryostat for condensed phase samples). However,
the Franck-Condon principle shows that we can access a number of excited vibrational
states during the electronic transition.
34
represented by the Morse potential curves. The ground electronic state S0 is a singlet
(paired-spin, or filled shell) configuration, typical of most neutral organic molecules. The
first single excited state, S1, is coloured blue. The lowest energy unpaired-spin
configuration is a triplet state labelled T1, shown at top right as the dark green curve.
Each of the three Morse potential curves have the first several vibrational levels shown
explicitly. Rotational levels are much more densely spaced, and though quite important, are
not shown.
35
Radiative processes (those which are "vertical" in energy transfer) are shown in solid lines
whereas non-radiative processes ("horizontal" energy transfer) are shown using dotted lines.
Indicative timescales are shown, although are molecule-dependant.
In principle the Jablonski diagram is similar to the transitions in the potential energy curves,
shown above, except the potential energy curves are usually not represented. A simple
Jablonski diagram for an organic molecule is shown above. Note that a similar diagram for an
inorganic compound will also include metal orbitals, so will be different in style.
Immediately following the transition, the diatomic molecule now resides on the potential
energy curve (surface, for a polyatomic molecule) with the geometry of the ground state, and
begins to vibrate with characteristics of the excited state v=3 level. Note that the blue S1
potential energy curve is broader than the dark red S0 curve. For this case, it means that the
excited state characteristic vibrational frequency will be lower than in the ground state.
36
3.4.1. Radiative versus Non-Radiative Excited State Decay Pathways
After vibrational relaxation has occurred over the time scale of some tens of femtoseconds to
many picoseconds, the molecule will be metastable in the S1,v=0 state for a time frame ranging
from hundreds of picoseconds (10-10 s) to hundreds of nanoseconds (10-7 s). From the S1,v=0
level, the eventual relaxation to the ground state can proceed by two general pathways: one
radiative, in which light is emitted from the molecular excited state, and the other non-
radiative, where a jump is made from the S1 excited-state electronic manifold to the S0
manifold. A third less probable possibility, intersystem crossing, is discussed below.
37
3.6.1. Internal Conversion: Importance to Life Processes
The measured excited state lifetimes of the five nucleic acid bases would be expected to be
about 10 nanoseconds based on their structural similarity to a large number of other organic
molecules. However, when illuminated by ultraviolet light in the 250-285 nm wavelength
range, the five nucleic acid bases cytosine, adenine, thymidine, guanine, and uracil decay by
a factor of about 20,000 times more rapidly than we might otherwise expect: the lifetimes of
the nucleic acid bases range from 0.29 to 0.72 picoseconds. It is precisely because of this
unique property of the nucleic acid electronic structure that life forms on this planet with
genetic material based on DNA/RNA are able to survive when our primary energy source is
derived from sunlight: the rapid internal conversion prevents other damaging excited-state
photochemical processes from occurring in DNA/RNA. When illumination by ultraviolet
light is too intense, then even this rapid molecular mechanism for dumping the UV light
energy fails: photochemistry occurs, especially oxidative damage to guanines; carcinogenic
lesions form, mutation rates skyrocket, and the organism dies from a number of causes.
Another major example of the importance of internal conversion to life processes is the
fact that tetrapyrrole molecules (including porphyrins, hemes, and chlorophyll a, shown
below) have very rapid relaxation from their higher-lying excited singlet states to a stable
lowest excited state from which all photochemical reactions and photophysical processes
(such as intermolecular energy transfer) can occur. A common feature of the excited-state
configurations of tetrapyrroles is that they have an extremely intense transition at the edge
of the UV-visible range (near 390-445 nm), with a molar extinction coefficient of about
106 M-1cm-1. This state is referred to not by its spectroscopic or electronic state label of S2
or S3, but rather as the Soret transition. The S2 and S1 states of chlorophyll a are called the
Qx and Qy transitions, respectively. Because these three transitions absorb strongly in the
near UV to blue and red spectral ranges, chlorophyll a appears bright green in colour, since
green is the only color of the visible spectrum not absorbed, hence giving grass and tree
leaves their green hue. Because the Soret excited state relaxes in about 1 picosecond via
internal conversion, then proteins are engineered to make use of energy absorbed from
sunlight by all three excited states, with the subsequent photochemical and photophysical
processes needing to be optimized only for the lowest energy excited state, S1.
Though intersystem crossing in general is not a high probability event, it is a mechanism that
links formally spin-forbidden transitions between states of different multiplicity. For
example, a spin- paired organic molecule in an excited singlet state can transform to a spin-
unpaired state by a flip of the lone electron remaining in the Highest Occupied Molecular
Orbital (HOMO). The probability for such a spin-flip transition is negligible, except in the
case where a vibronic energy level of the singlet is nearly degenerate with the energy of a
triplet vibronic state. In the diagram above, The S1,v=2 state has been drawn to be only
marginally higher in energy than the T1,v=4 state. When such a situation occurs, then the
probability for the spin-flip intersystem crossing process is greatly enhanced. When a triplet
state such as the green potential curve labelled T1 shown above is populated by intersystem
crossing, the vibrational relaxation process will normally occur quite rapidly, lowering the
energy of the triplet T1 state to the bottom of its vibronic potential energy well T1,v=0. As
38
shown above, the T1,v=0 state lies substantially below the S1,v=0 state, making a reverse
intersystem crossing process have a very much lower probability than in the forward
direction. Thus, the only decay channel for T1,v=0 is to await the very low probability event
that the T1,v=0 state can return to the S0 vibronic manifold. As discussed immediately above,
the T1,v=0 excited-state decay can be either radiative or non-radiative. Unless there is an
accidental near degeneracy (which occurs less frequently than in the excited state case, as one
can see by thinking carefully about the density of states in an enharmonic Morse potential for
S1, T1, and S0) the T1 state can be quite long-lived. At room temperature, triplet states may
last for milliseconds, while at reduced temperatures, the triplet state can persist for minutes to
hours.
3.9. Photosensitization
Photosensitization is the process of initiating a reaction through the use of a substance
capable of absorbing light and transferring the energy to the desired reactants. The technique
is commonly employed in photochemical work, particularly for reactions requiring light
sources of certain wavelengths that are not readily available. A commonly used sensitizer is
mercury, which absorbs radiation at 1849 and 2537 angstroms; these are the wavelengths of
light produced in high-intensity mercury lamps. Also used as sensitizers are cadmium; some
of the noble gases, particularly xenon; zinc; benzophenone; and a large number of organic
dyes.
In a typical photosensitized reaction, as in the photodecomposition of ethylene to acetylene
and hydrogen, a mixture of mercury vapour and ethylene is irradiated with a mercury lamp.
The mercury atoms absorb the light energy, there being a suitable electronic transition in the
atom that corresponds to the energy of the incident light. In colliding with ethylene
39
molecules, the mercury atoms transfer the energy and are in turn deactivated to their initial
energy state. The excited ethylene molecules subsequently undergo decomposition. Another
mode of photosensitization observed in many reactions involves direct participation of the
sensitizer in the reaction itself.
40
near the bottom of the upper potential curve, and follows a vertical arrow down (F), until it
strikes the lower potential curve. Again, it does not hit it in its deepest point, so that some
excitation energy becomes converted into vibrational energy. The cycle absorption-emission
thus contains two periods of energy dissipation. Because of this, the fluorescence arrow (F) is
always shorter (that is, the fluorescence frequency is lower) than that of absorption (A). In
other words, the wavelengths of the fluorescence band are longer than of the absorption band.
This displacement of fluorescence bands towards the longer wavelengths compared to the
absorption bands (Stokes' shift) was a long-established experimental fact before the Franck-
Condon principle provided its interpretation. Obviously, the extent of the shift depends on the
difference between the two potential curves.
Figure 5: Frank-Condon Principle. Potential energy curves for the ground state and an excited
state of a diatomic molecule. (r, interatomic distance; A, absorption; F, fluorescence; numbers
indicate vibrational states.)
41
his student Hertha Sponer, who was then at the University of California at Berkeley on an
International Education Board Fellowship. She generously shared the proofs with Condon; he
was able to generalize Franck's ideas (Condon, 1926). Condon (1947) states: "This work was
all done in a few days. Doctor Sponer showed me Franck's paper one afternoon, and a week
later all the quantitative work for my 1926 paper was done."
Figure 6: The Stokes' shift (displacement of fluorescence band compared to the absorption band
of a molecule). Approximate mirror symmetry of the two bands exists when the shapes of the
potential curves in the ground state and the excited state are similar.
42
4.0. SUMMARY
Light absorption can result in the formation of an (electronically) excited state, which has
different chemical properties to the ground state. The intensity and shape of absorption
spectra are a result of the nature of excitation between ground and excited states. Various
processes result in the deactivation of the excited state. The timescales of these indicate their
efficiency, and we will look at these in more detail in future posts.
6.0. REFERENCES
1. Gilbert, A. and Baggott, J. E., Essentials of molecular photochemistry, Blackwell
Scientific: London, 1991.
2. Turro, N. J., Ramamurthy, V. and Scaiano, J. C., Principles of molecular
photochemistry: an introduction, University Science Books: Sausalito, 2009. Despite
the title, a detailed text with lots on the various photophysical processes that occur on
light absorption. These three authors are among the best known photochemists today.
Turro’s classic, Modern Molecular Photochemistry, was for a long time the bible for
photochemistry.
3. http://www.life.illinois.edu/govindjee/biochem494/Abs.html
4. http://www.britannica.com/EBchecked/topic/458153/photosensitization
43
UNIT 4 – SELECTION RULES AND PHOTOPHYSICAL PARAMETERS
1.0. INTRODUCTION
We have looked at the way photons are absorbed. Photons of UV and visible light cause
electrons to promote between orbitals. In this Unit, we shall look at the way this photon
absorption is analysed by spectroscopists. When a photon is absorbed or generated, we must
conserve the total angular momentum in the overall process. So we must start by looking at
some of the ‘rules’ that allow for intense UV-visible bands (caused by electronic motion).
Selection rules are a set of restrictions governing the likelihood that a physical system will
change from one state to another or will be unable to make such a transition. Selection rules,
accordingly, may specify "allowed transitions," those that have a high probability of
occurring, or "forbidden transitions," those that have minimal or no probability of occurring.
It is advisable to employ a high-power lamp when performing a photochemical reaction
because it produces more photons than a low-power lamp. Its flux is greater. When we
looked at the laws of photochemistry, we saw how the second law stated the idea that when a
species absorbs radiation, one particle is excited for each quantum of radiation absorbed. This
(hopefully) obvious truth now needs to be investigated further. The ‘quantum yield’ Φ is a
useful concept for quantifying the number of molecules of reactant consumed per photon of
light. It may be defined mathematically by
2.0. OBJECTIVES
After studying this Unit, you should be able to:
• Explain the concept of selection rules
• Define and carry out simple calculations on quantum yields
• Determine the number of photons absorbed by a sample in a photochemical
process
• Define the lifetime of an excited species
• Derive an expression for the lifetime of an excited species
• Calculate the rate constants for the various photophysical parameters
• Use the Stern-Volmer equation to analyze the fluorescence quenching of a
fluorophore
44
only, which means they may occur in practice but with low probability. Light absorption is a
resonant process; hence the most fundamental condition for absorption is that the energy of
the incoming photon must match the difference in energy between the two energy states
involved in the transition (∆E = hν). In addition to this energy matching, the probability of an
electronic transition is predicted using a set of selection rules, which may be summarized as
follows:
number of events
φ=
number of photons absorbed
This definition emanates from the first and second laws of photochemistry, which proposed
that for any photochemical process to take place, there must be absorption of photons, and
that one photon activates only one molecule. Many factors, intrinsic and extrinsic to the
system, can influence the efficiency of a photochemical process. Quantum yield is a measure
of the efficiency of such processes after light absorption. The efficiencies of all
photochemical and photophysical processes are quantified by the quantum yield.
Its value can lie anywhere in the range 10−6 to 106. A value of 10−6 implies that the photon
absorption process is very inefficient, with only one molecule absorbed per million photons.
In other words, the energetic requirements for reaction are not being met. Conversely, a
quantum yield Φ of greater than unity cannot be achieved during a straightforward
photochemical reaction, since the second law of photochemistry clearly says that one photon
is consumed per species excited. In fact, values of Φ > 1 indicate that a secondary reaction(s)
has occurred. A value of Φ > 2 implies that the product of the photochemical reaction is
consumed by another molecule of reactant, e.g. during a chain reaction, with one photon
generating a simple molecule of, say, excited chlorine, which cleaves in the excited state to
generate two radicals. Each radical then reacts in propagation reactions until the reaction
mixture is exhausted of reactant.
To help clarify the situation, we generally define two types of quantum yield: primary and
secondary. The magnitude of the primary quantum yield refers solely to the photochemical
formation of a product so, from the second law of Photochemistry, the value of Φprimary
cannot be greater than unity. The so-called secondary quantum yield refers to the total
number of product molecules formed via secondary (chemical) reactions; its value is not
limited. The primary quantum yield should always be cited together with the photon pathway
occurring: it is common for several possible pathways to coexist, with each characterized by
a separate value of Φ. As a natural consequence of the second law of photochemistry, the
sum of the primary quantum yields cannot be greater than unity.
The quantum yield of a photophysical process is directly related to the ‘allowedness’ of the
process. For example, phosphorescence (T→S transition) is a spin-forbidden process; hence
its quantum yield is expected to be small.
The quantum yields for some photophysical and photochemical processes are defined thus:
46
no of fluorescing molecules
Fluorescence quantum yield: φF =
no of photons absorbed
no of moleculeundergoingintersystem crossing
Intersystem crossing: φISC =
no of photonsabsorbed
n o of Phosphorescing molecules
Phosphorescence: φP =
n o of photons absorbed
Two pieces of information are needed to determine the number of photons absorbed by a
sample:
1. The power (or energy) of the incident light
Light emanating from a source (laser, flash light, incandescent light bulb, etc) is characterized
by its power output (e.g., 80 W, 80 Js-1).
Photons have no mass, but they have energy E = hν = . Here h = 6.626 x10-34 Js is a
universal constant called Planck's constant. The energy of each photon is inversely
proportional to the wavelength of the associated electromagnetic wave. The shorter the
wavelength, the more energetic is the photon, the longer the wavelength, the less energetic is
the photon.
Knowing these two quantities, then the number of photons incident photons (Nincident) is given
as:
47
The number of photons absorbed (Nabsorbed) is given as
Where α is the fraction of incident photons absorbed i.e., the efficiency of absorption. α is
sometimes given as %-absorption.
Example 1:
Calculate the number of photons emitted by a 100 W yellow lamp in 1.0 s. Take the
wavelength of yellow light as 560 nm and assume 100 % efficiency.
Solution:
Power = 100 W = 100 J s-1
Time = 1.0 s
Example 2:
When a sample of 4-heptanone was irradiated with 313 nm light with a power output of 50 W
under conditions of total absorption for 100 s, it was found that 2.8 x10-3 mol C2H4 was
formed. What is the quantum yield for the formation of ethane?
Solution:
No. of moles of C2H4 formed = 2.8 x10-3 mol
Power = 50 W = 50 J s-1
Time = 100 s
48
= 5000 J
S0 + hν → S1 Rate = Ia Absorption
S1 → S0 + hνF Rate = kF[S1] Fluorescence
S1 −−→ S0 + heat Rate = kIC[S1] Internal conversion
S1 −−→ T1 Rate = kISC[S1] Intersystem crossing
The radiative lifetime, τ0, is a measure of the probability of emission, which is related to the
probability of absorption. The radiative lifetime is represented by:
1
τ0 =
kF
49
lifetime if fluorescence was the only process deactivating the excited state, and it is the
reciprocal of the first order rate constant of fluorescence. Following excitation, the molecule
will also relax by internal conversion and intersystem crossing, in addition to fluorescence; so
that the rate of decay of the singlet excited state is the sum of these three decay processes.
− d[S1 ]
= (k F + k IC + k ISC )[S1 ]
dt
The lifetime of the excited state (S1) is the reciprocal of the first order rate constant for decay.
1
τF =
k F + k IC + k ISC
However, τ 0 = 1
kF
There
The triplet state (T1) formed can undergo further relaxation processes:
Typically, the rate of triplet formation is much faster than the rate of triplet decay, i.e., kISC >
(kP + k′ISC).
As in the case of the singlet state,
− d[T1 ]
= (k P + k ′ISC )[T1 ]
dt
And the phosphorescence (triplet) lifetime is given by:
50
1
τT =
(k P + k ′ISC )
In all cases, the excited triplet state is longer lived than the singlet counterpart because of the
decay (radiative or non-radiative) of the T1 to the S0 state is forbidden. Table X gives a
description of the common photophysical processes.
- dA
Rate of decay = = k d [A]
dt
kd is the first order decay constant. Rearranging this equation, we have:
dA
= −k d dt
[A]
Integrating,
A 1 t
∫A0 [A]
dA = − k d ∫ dt
0
and
In[A] – In[A]o = -kdt
[ A]
ln = −k d t
[ A] 0
51
[ A] 0
t = τ, when [ A] =
e
Substituting, we have:
1
ln = − k d τ
e
lne
τ=
kd
And
log e e 1
τ= =
kd kd
kF
ΦF =
k F + k IC + k ISC
1
However, it is also known that τ F =
k F + k IC + k ISC
52
Therefore, Φ F = k F .τ F
It is known that
1 1
τF = ; and τ 0 =
k F + k IC + k ISC kF
kF τ
Therefore, it follows that = F = ΦF
k F + k IC + k ISC τ 0
If the lifetime of an excited state and the quantum yields of all processes deactivating it are
known, it is possible to calculate the rate constants for the deactivating processes.
The following equations give the expressions for rate constants for the intrinsic processes
(fluorescence, F; internal conversion, IC and intersystem crossing, ISC), which deactivate the
excited singlet state of a molecule:
ΦF
kF =
τF
Φ IC
k IC =
τF
Φ ISC
k ISC =
τF
Question:
For naphthalene in a glassy matrix at 77 K excited to the S1 state, the quantum yield of
fluorescence is 0.20, the quantum yield of triplet formation is 0.80, and the quantum yield of
phosphorescence is 0.018.
a) Using the measured lifetime of fluorescence of 96 ns, determine the rate constant for
intersystem crossing from S1 to T1.
b) From the measured phosphorescence lifetime of 2.6 s, determine the rate constant for
intersystem crossing from T1 to S0.
Answer:
a) From the S1 state,
Φ ISC Φ T 0.8
k ISC = = = −8
= 8.33 x106 s −1
τF τ F 9.6 x10
53
b) From the T1 state,
Φ′ISC 0.792
∴ k ′ISC = = = 0.305 s −1
τT 2.6
Quenching depends on the ability of the fluorophore to transfer energy to the quencher
without the emission of light. Collisional quenchers do this by partaking in close molecular
interactions with the fluorophore,
When only the three intrinsic processes (F, IC and ISC) deactivate the excited singlet state,
i.e., no external factor contributing to the singlet decay; the fluorescence lifetime of a
fluorophore can be expressed as:
1
= k F + k IC + k ISC
τ 0F
However in the presence of a reactant (Q, also known as a quencher) that intercepts the S1
state, the following excited state reaction takes place:
→
k
S1 + Q Q
S0 + Q *
The rate law for this reaction is written as:
Rate = kQ[S1][Q]
Where kQ is the bimolecular quenching constant; [S1] and [Q] are the concentrations of the S1
state and the quencher respectively.
Assuming that the reaction is pseudo-unimolecular with [Q] >> [S1], we can state that:
Rate = k′[S1]
Where
k′ = kQ[Q]
54
As a result of this quenching reaction, the fluorescence lifetime of the fluorophore is lowered;
the quenching term is introduced into the expression for the S1 state deactivation, and we now
have:
1
= k F + k IC + k ISC + k Q [Q]
τF
Taking ratios,
τ 0F k F + k IC + k ISC + k Q [Q]
=
τF k F + k IC + k ISC
Simplification yields:
τ 0F
= 1 + k Q [Q]. τ 0F
τF
A vital assumption made in the treatment of fluorescence quenching data is that the rate
constants for the intrinsic processes do not change in the presence of a quencher. This implies
that for any system,
τ 0F Φ 0F I 0
= =
τF ΦF I
This is the familiar Stern-Volmer (S-V) equation, which is usually written as:
I0
= 1 + K SV [Q]
I
Where kQ (M-1 s-1) is the bimolecular quenching rate constant; the Stern-Volmer constant
(KSV, M-1) is defined by as:
K SV = k Q τ 0F
I0
A plot of versus [Q] should give a straight line with intercept 1 and slope KSV. The
I
observation of a straight line from this plot would indicate that the quenching process is
solely by a collisional mechanism (dynamic quenching).
55
4.0. SUMMARY
A selection rule is a quantum mechanical rule that describes the types of quantum mechanical
transitions that are permitted. The familiar selection rules are: spin selection rule, LaPorte
selection rule, Franck-Condon selection rule and orbital overlap section rule.
The quantum yield (Φ) of a radiation-induced process is the number of times a specific
event occurs per photon absorbed by the system.
Two pieces of information are needed to determine the number of photons absorbed by a
sample:
Three types of lifetime exist in photochemistry: fluorescence lifetime (τF), triplet lifetime (τT)
and the radiative lifetime (τ0). By definition, τ0 is the lifetime of an excited molecule in the
absence of radiationless transitions. The radiative lifetime is not the actual lifetime of the
excited state; it is the lifetime if fluorescence was the only process deactivating the excited
state.
The fluorescence of a substance is said to be quenched if the addition of another substance to
it reduces the intensity of fluorescence, provided that no chemical reaction occurs between
the fluorescing substance (fluorescer or fluorophore) and the quenching material (quencher).
According to Stern and Volmer, the quenching process is a reaction of the second order,
which competes with all other molecular and radiative processes, and is subject to the
equation:
I0
= 1 + k SV [Q]
I
2. The quantum yield for a photochemical reaction is 0.91. The absorbing substance
was exposed to 320 nm radiation from a 87.5 W source. The intensity of the
transmitted light was 0.257 that of the incident light. As a result of the irradiation,
0.324 mol of the absorbing substance decomposed. For what length of time must the
irradiation have persisted?
3. Derive the Stern-Volmer equation for the reaction of a fluorophore (S1*) with a
quencher (Q); after which the fluorophore was deactivated and the quencher excited.
56
5. The change in fluorescence intensity of a zinc(II) phthalocyanine derivative varies
with the concentration of benzoquinone (BQ) quencher in DMF is as follows:
6.0. REFERENCES
1. N. J. Turro, Molecular Photochemistry, Benjamin, New York, 1967.
2. J. R. Lakowicz, Principles of Fluorescence Spectroscopy, Springer, New York,
2006.
57
UNIT 5 - LASERS
1.0. INTRODUCTION
Lasers are devices that produce intense beams of light which are monochromatic, coherent,
and highly collimated. The wavelength (colour) of laser light is extremely pure
monochromatic) when compared to other sources of light, and all of the photons (energy) that
make up the laser beam have a fixed phase relationship (coherence) with respect to one
another. Light from a laser typically has very low divergence. It can travel over great
distances or can be focused to a very small spot with a brightness which exceeds that of the
sun. Because of these properties, lasers are used in a wide variety of applications in all walks
of life.
The basic operating principles of the laser were put forth by Charles Townes and Arthur
Schalow from the Bell Telephone Laboratories in 1958, and the first actual laser, based on a
pink ruby crystal, was demonstrated in 1960 by Theodor Maiman at Hughes Research
Laboratories. Since that time, literally thousands of lasers have been invented (including the
edible “Jello” laser), but only a much smaller number have found practical applications in
scientific, industrial, commercial, and military applications. The helium neon laser (the first
continuous-wave laser), the semiconductor diode laser, and air-cooled ion lasers have found
broad OEM application. In recent years the use of diode-pumped solid-state (DPSS) lasers in
OEM applications has been growing rapidly. The term “laser” is an acronym for (L)ight
(A)mplification by (S)timulated (E)mission of (R)adiation.
2.0. OBJECTIVES
After studying this Unit, you should be able to:
58
nature of light and absorption and emission of light. Atoms emit radiation. For example,
"excited" neon atoms in a neon sign emit light, which is normally radiated in random
directions at random times. The result is incoherent light (a technical term for a jumble of
photons going in all directions). To generate a coherent light (nearly monochromatic and
going in one precise direction); it is imperative to find the right atoms and an environment
which would make the all light given up to go in one direction.
There are many different types of lasers, with output wavelengths ranging from ultraviolet to
far infra-red. Lasers are broadly classified into solid, liquid and gas lasers. Most solid and gas
lasers are only able to produce photons at a fixed wavelength, and this tends to limit their
utility for chemical applications. Liquid lasers (which contain dye solutions and nearly
operate mostly in the visible and near UV) on the other hand can be adjusted (tuned) over a
certain wavelength range. A major advantage of lasers over other light sources is that they are
capable of producing highly energetic and nearly monochromatic photons. The processes that
go on inside them differing greatly from one laser type to another, hence, it is easy to become
distracted by detail that might apply to one type of laser only. The features described here are
those that lasers have in common.
3.1.1. Monochromaticity
Laser light consists of essentially one wavelength, having its origin in stimulated emission
from one set of atomic energy levels.
All light consists of waves travelling through space. The colour of the light is determined by
the length of those waves, as illustrated in Figure 1.
59
Wavelength is the distance over which the wave repeats itself and is represented by the
Greek letter (lambda). Each colour of visible light has its own characteristic wavelength.
White light consists of a mixture of many different wavelengths. A prism can be used to
disperse white light into its component wavelengths (colours), as in Figure 2.
All common light sources emit light of many different wavelengths. White light contains all,
or most, of the colours of the visible spectrum. Ordinary coloured light consists of a broad
range of wavelengths covering a particular portion of the visible-light spectrum. A green
traffic light, for example, emits the entire green portion of the spectrum, as well as some
wavelengths in the neighbouring yellow and blue regions.
The beam of a helium-neon gas laser, on the other hand, is a very pure red colour. It consists
of an extremely narrow range of wavelengths within the red portion of the spectrum. It is said
to be nearly "monochromatic," or nearly "single-coloured." Near-monochromaticity is a
unique property of laser light, meaning that it consists of light of almost a single wavelength.
Perfectly monochromatic light cannot be produced even by a laser, but laser light is many
times more monochromatic than the light from any other source. In some applications,
special techniques are employed to further narrow the range of wavelengths contained in the
laser output and, thus, to increase the monochromaticity.
3.1.2. Directionality
Figure 3 depicts light being emitted from a light bulb in all directions. All conventional light
sources emit light in this manner. Devices such as automobile headlights and spotlights
contain optical systems that collimate the emitted light, such that it leaves the device in a
directional beam; however, the beam produced always diverges (spreads) more rapidly than
the beam generated by a laser.
60
Figure 3: Conventional source
61
3.1.3. Coherence
Figure 5 depicts a parallel beam of light waves from an ordinary source traveling through
space. None of these waves has any fixed relationship to any of the other waves within the
beam. This light is said to be "incoherent," meaning that the light beam has no internal order.
Figure 6 illustrates the light waves within a highly collimated laser beam. All of these
individual waves are in step, or "in phase," with one another at every point. "Coherence" is
the term used to describe the in-phase property of light waves within a beam.
Just as laser light cannot be perfectly monochromatic or perfectly directional, it cannot have
perfect coherence; yet laser light is far more coherent than light from any other source.
Techniques currently in use greatly improve the coherence of light from many types of lasers.
Coherence is the most fundamental property of laser light and distinguishes it from the light
from other sources. Thus, a laser may be defined as a source of coherent light. The full
importance of coherence cannot be understood until other concepts have been introduced, but
evidence of the coherence of laser light can be observed easily.
62
In Figure 7, the beam of a low-powered laser strikes a rough surface, such as paper or wood,
and is reflected in all directions. A portion of this light reaches the eye of an observer several
meters away. The observer will see a bright spot that appears to be stippled with many bright
and dark points. This "speckled" appearance is characteristic of coherent light, and is caused
by a process called "interference," which will be discussed in a later module.
Figure 7
An atom is the smallest particle of an element that retains the characteristics of the element.
An atom consists of a positive nucleus surrounded by a "cloud" of negative electrons. All
neutral atoms of a given element have the same number of positive charges (protons) in the
nucleus and negative charges (electrons) in the cloud. The energy content of atoms of a
particular type may vary, however, depending on the energies contained by the electrons
within the cloud.
Each type of atom can contain only certain amounts of energy. When an atom contains the
lowest amount of energy that is available to it, the atom is said to be in its "atomic ground
63
state." If the atom contains additional energy over and above its ground state, it is said to be
in an "excited atomic state."
Figure 8 is a simplified energy-level diagram of an atom that has three energy levels. This
atom can contain three distinct amounts of energy and no others. If the atom has an energy
content of El, it is in the atomic ground state and is incapable of releasing energy. If it
contains energy content E2 or E3, it is in an excited state and can release its excess energy,
thereby dropping to a lower energy state. Real atoms may have hundreds or even thousands
of possible distinct energy states. The three-level mode is utilized here for purposes of clarity.
An atom in an excited state is unstable and will release spontaneously its excess energy and
return to the ground state. This energy release may occur in a single transition or in a series of
transitions that involve intermediate energy levels. For example, an atom in state E3 of Figure
8 could reach the ground state by means of a single transition from E3 to El, or by two
transitions, first from E3 to E2 and then from E2 to E1. In any downward atomic transition, an
amount of energy equal to the difference in energy content of the two levels must be released
by the atom. In many cases, this excess energy appears as a photon of light. A photon is a
quantum of light having a characteristic wavelength and energy content; in fact, the
wavelength of the photon is determined by its energy. A photon of longer wavelength (such
as that for red light) possesses less energy than one of shorter wavelength (such as that for
blue light), as illustrated in Figure 9.
64
Figure 9: Spontaneous emission
In ordinary light sources, individual atoms release photons at random. Neither the direction
nor the phase of the resulting photons is controlled in any way, and many wavelengths
usually are present. This process is referred to as "spontaneous emission" because the atoms
emit light spontaneously, quite independent of any external influence. The light produced is
neither monochromatic, directional, nor coherent.
The coherent light of the laser is produced by a "stimulated-emission" process (Figure 10). In
this case, the excited atom is stimulated by an outside influence to emit its energy (photon) in
a particular way.
65
Figure 10: Stimulated emission
The stimulating agent is a photon whose energy (E3–E2) is exactly equal to the energy
difference between the present energy state of the atom, E3 and some lower energy state, E2.
This photon stimulates the atom to make a downward transition and emit, in phase, a photon
identical to the stimulating photon. The emitted photon has the same energy, same
wavelength, and same direction of travel as the stimulating photon; and the two are exactly in
phase. Thus, stimulated emission produces light that is monochromatic, directional, and
coherent. This light appears as the output beam of the laser.
Figure 11 illustrates another process that occurs within a laser. Here, a photon strikes an atom
in energy state E2 and is absorbed by that atom. The photon ceases to exist; and its energy
appears as increased energy in the atom, which moves to the E3 energy level. The process of
absorption removes energy from the laser beam and reduces laser output.
66
3.2.5. Population Inversion
In order for a laser to produce an output, more light must be produced by stimulated emission
than is lost through absorption. For this process to occur, more atoms must be in energy level
E3 than in level E2, which does not occur under normal circumstances. In any large collection
of atoms in matter at any temperature T, most of the atoms will be in the ground state at a
particular instant, and the population of each higher energy state will be lower than that of
any of the lower energy states. This is called a "normal population distribution."
Under "normal" circumstances, each energy level contains many more atoms than the energy
level just above it, and so on up the energy lever ladder. For example, at room temperature, if
there are No atoms in the ground state of Neon (He-Ne laser) there are only 10-33No atoms in
the first excited state, even fewer in the second excited state and so forth. The population of
the ascending energy levels decreases exponentially.
Thus, in any large collection of atoms in matter at any temperature T, most of the atoms will
be in the ground state at a particular instant, and the population of each higher energy state
will be lower than that of any of the lower energy states. This is called a "normal population
distribution."
A population inversion exists whenever more atoms are in an excited atomic state than in
some lower energy state. The lower state may be the ground state, but in most cases it is an
excited state of lower energy. Lasers can produce coherent light by stimulated emission only
if a population inversion is present. And a population inversion can be achieved only through
external excitation of the atomic population.
67
3.3.1. Amplification
A laser consists of a pumped active medium positioned between two mirrors (Figure 12). The
purpose of the mirrors is to provide what is described as 'positive feedback'. This means
simply that some of the light that emerges from the active medium is reflected back into it for
amplification. One of the mirrors is a total reflector, and reflects almost all of the light that
falls upon it. The other mirror, known as the output coupler, is only partially reflective. The
light that is not reflected being transmitted through the mirror, and constitutes the output
beam of the laser.
The process of light amplification could be accounted for by a consideration of the interaction
of light with individual atoms within the active medium. Light absorption is a resonant
process, and so there will be no absorption if there is no pair of energy states such that the
photon energy can elevate the system from the lower to the upper state, i.e., there must be an
energy matching between the photon and the separation of the two electronic states. If an
electron is already in an excited state (an upper energy level, in contrast to its lowest possible
level or "ground state"), then an incoming photon for which the quantum energy is equal to
the energy difference between its present level and a lower level can kindle a transition to that
lower level, producing a second photon of the same energy. This process is termed
“stimulated emission”. When a sizable population of electrons resides in upper levels, this
condition is called a "population inversion", and it sets the stage for stimulated emission of
multiple photons. This is the precondition for the light amplification that occurs in a laser,
and since the emitted photons have a definite time and phase relation to each other, the light
has a high degree of coherence. The stimulated emission of light is the crucial quantum
process necessary for the operation of a laser.
68
population inversion can occur. In order to establish a population inversion, the upper state
must be populated by pump energy, and the lower state must be depopulated. This could be
achieved by using either the 3-level laser or the 4-level laser.
Excited state
hν 2-Level system
G round state
In the 3-level scheme, the particles are first excited to an excited state higher in energy than
the upper laser state (Figure 14). The particles then quickly decay down into the upper laser
state. It is important for the pumped state to have a short lifetime for spontaneous emission
compared to the upper laser state. The upper laser state should have as long a lifetime (for
spontaneous emission) as possible, so that the particles live long enough to be stimulated and
thus contribute to the gain. The gain is the factor by which the intensity of the light is
increased by the active (amplifying) medium. In this 3-level laser system, the lower state is
the ground state, so in order to depopulate it; a large amount of pump energy must be put in
so that the ground state is actually in lower concentration than the excited state. The only way
to depopulate the ground state is to put in more and more pump energy.
3
3 Metastable state
Metastable state
Pump LASER
Pump
LASER 4
1 1
Ground state Ground state
In the case of the “4-level” scheme (Figure 14), only a modest pump energy may be
sufficient to establish a population inversion between higher laser state (3) and lower laser
69
state (4) if the upper state is relatively long lived (metastable) and lower state is relatively
short lived (unstable). Laser transition takes place between the states (3) and (4) and so a
rapid depopulation of state (3) to the ground state is required to ensure that the upper level is
always full and the lower level always (almost) empty (Figure 15).
E x c ite d s ta te
G ro u n d s ta te
Pump
E x c ite d s ta te
G r o u n d s ta te
The followings are some important areas where lasers find huge application:
Scientific
Laser spectroscopy
Photochemistry
Photophysics
Raman spectroscopy
Medical
Cosmetic surgery (tattoo, hair, scar, stretch mark, sunspot, wrinkle & birthmark
removal)
Eye surgery (LASIK, etc...)
Laser scalpel (gynecological, urology, laparoscopic)
Dental procedures
Imaging
Military
"Death ray": A hand-held device that might replace the gun as a weapon for
infantry
"Laser cannon": Able to destroy tanks, ships and aircraft
70
Laser sight (to enhances the targetting of other weapons systems)
Saber 203 Laser Illuminator (U.S. Air Force)
laser target designator used to indicate a target for a laser guided munition, e.g.,
missile
Industrial and Commercial
Cutting, welding, marking,
Isotope separaton
Rangefinder / surveying,
LIDAR / pollution monitoring,
CD/DVD player,
Laser printing, scanners,
Laser engraving of printing plates,
Laser pointers, holography, laser light displays
Photolithography,
Optical communications.
Optical tweezers
4.0. SUMMARY
The laser is a light source that exhibits unique properties and a wide variety of applications.
Lasers are used in welding, surveying, medicine, communication, national defence, and as
tools in many areas of scientific research. Many types of lasers are commercially available
today, ranging in size from devices that can rest on a fingertip to those that fill large
buildings. All these lasers have certain basic characteristic properties in common.
A laser is a coherent and highly directional radiation source. LASER stands for Light
Amplification by Stimulated Emission of Radiation.
The gain medium can be solid, liquid, or gas and the pump source can be an electrical
discharge, a flash lamp, or another laser. The specific components of a laser vary depending
on the gain medium and whether the laser is operated continuously (cw) or pulsed.
If light of the right colour hits an atom, it will bump an electron up to a higher energy level.
And later the electron falls back down, giving off light of the same colour in some random
direction.
But when a photon hits an atom that is already excited, the atom releases a new photon that is
completely identical to the incoming photon; same colour, going in the same direction. We
call this process "stimulated emission". This is basic of all lasers.
71
5.0. TUTOR-MARKED ASSIGNMENTS
1. Define the following properties of laser light:
1. Monochromaticity
2. Directionality
3. Coherence
6.0. REFERENCES
1. http://utopia.cord.org/cm/leot/course01_mod01/mod01-01frame.htm
2. Ogunsipe, A.O., “Photophysical and Photochemical Studies on Non-transition Metal
Phthalocyanone Derivatives”, Ph.D thesis, Rhodes University, 2004.
72
UNIT 6 – PHOTOCHEMICAL REACTIONS
1.0. INTRODUCTION
The process by which a photochemical reaction is carried out is called photolysis. Photolysis
is usually initiated by infrared, visible, or ultraviolet light. A primary photochemical reaction
is the immediate consequence of the absorption of light. Subsequent chemical changes are
called secondary processes.
Photochemical reactions are utilized in synthetic chemistry to produce various organic
molecules. In addition, many common processes are photochemical in nature and have
important applications. For example: photosynthesis involves the absorption of light by the
chlorophyll in plants to produce carbohydrates from carbon dioxide and water.
Photography uses the action of light on grains of silver chloride or silver bromide to produce
an image. Ozone formation in the upper atmosphere results from action of light on oxygen
molecules. Solar cells, which are used to power satellites and space vehicles, convert light
energy from the sun to chemical energy and then release that energy in the form of electrical
energy.
In this unit we shall focus chiefly on the nature and behaviour of the electronic excited states
formed when a photon is absorbed by a chromophoric functional group. As a rule, such
excitation results in a change in molecular orbital occupancy, an increase in energy, and
changes in local bonding and charge distribution.
2.0. OBJECTIVES
73
3.0. MAIN CONTENT
2. Since different coloured radiations in the range of visible light have different frequencies
and hence different energies, therefore all radiations may not be able to initiate a particular
reaction. For example, a photon of violet light has highest frequency and hence the highest
energy. Hence a reaction which is initiated by violet light may not be initiated by other
colored radiations of visible light. On the other hand, a photon of red light has lowest
frequency and energy. Therefore a reaction that can be initiated by red light can be initiated
by all other radiations as well.
3. Temperature has very little effect on the rate of a photochemical reaction. Instead, the
intensity of light has marked effect on the rate of photochemical reaction.
5. There are many substances which do not react directly when exposed to light. However, if
another substance is added, the photochemical reaction starts
1. The excited states are rich in energy. Therefore reactions may occur that are highly
endothermic in the ground state. Using the equation E = h x ν we can correlate light of a
wavelength of 350 nm with an energy of 343 kJ/mol.
2. In the excited state anti-bonding orbitals are occupied. This may allow reactions which are
not possible for electronic reasons in the ground state.
3. Photochemical reaction can include singlet and triplet states; thermal reactions usually only
show singlet states. In photochemical reaction intermediates may be formed which are not
accessible at thermal
74
3.1.3. Factors Determining Outcome of a Photochemical Reaction
Reaction medium may directly modify the potential energy surfaces of the ground and
excited states and hence affect the photo-reactivity. The outcome of some reactions changes
dramatically when solvent polarity and hydrogen bonding capacity are changed. The
protolytic photo-dissociation of 1-naphthol is completely suppressed in aprotic solvents
because of unfavourable solvation energies both for the anion and proton. Under such
conditions, proton transfer reaction cannot compete with the deactivation.
Solvent viscosity will strongly affect photoreactions where the encounter of two reactants or
a substantial structural change is required. In highly viscous or solid solutions the loss of
excitation via light emission or unimolecular non-radiative deactivation is more probable than
a chemical modification of the excited species. On the other hand, slow diffusion in viscous
solutions may prevent self-deactivation of the triplet state via a bimolecular process called
triplet-triplet annihilation and enhance the efficiency of a photoreaction from this state.
Triplet-triplet annihilation belongs to electronic-energy transfer processes, which may be
classified as quenching of excited states. Quenching rate is a very important factor in
discussing effects of
Formation of Ozone
Ozone (O3) is formed in the upper atmosphere from ordinary oxygen (O2) gas molecules
according to the reaction:
After a quantum of ultraviolet light is absorbed (step 1), the excited oxygen molecule
dissociates into two oxygen atoms (step 2). An oxygen atom then reacts with O2 to form
ozone (step 3).
76
another unstable radical. This new radical can now attack another molecule, thereby
reforming the original radical, which can now begin a new cycle of events.
The hydrogen-chlorine reaction is an example of a chain reaction. The overall reaction
between hydrogen and chlorine gases in the presence of violet or ultraviolet light forms
hydrogen chloride; it is given by This reaction actually proceeds according to the following
series of steps:
According to the above mechanism, a suitable quantum of light dissociates a chlorine
molecule into atoms (step 1). The reactive Cl atom attacks a hydrogen molecule to yield
hydrogen chloride and a hydrogen atom (step 2). The reactive hydrogen atom attacks a
chlorine molecule, which regenerates the Cl atom (step 3). This chlorine atom can then react
with another H2 molecule according to step 2, beginning a new cycle of steps. Steps 2 and 3
will occur many times until either of the two reactants, H2 and Cl2, is completely consumed
or until the H or Cl radicals attack a new substance that has been introduced into the reaction
chamber.
There exists a plethora of photoreactions practically for each class of chemical compounds.
These reactions may be categorized according to chemical composition and structure. They
may also be classified under different types by using theoretical models for the description of
the excited state(s) or structure of the potential energy surface. However, for our introductory
discussion it seems to be more appropriate just to consider some examples classified by
general reaction types (Figure 3.1).
77
3.3.2. Cycloaddition of unsaturated molecules
Two thymines can react to form a ring product, the thymine dimer, an important class of
products formed in DNA by UV radiation.
3.3.3. Photofragmentation
The side chain of riboflavin can split off to form lumiflavin.
78
3.3.4. Photooxidation
Singlet oxygen is an easily available reagent. It can be generated from triplet oxygen in
many solvents by a broad variety of sensitizers. The reaction of organic compounds with
singlet oxygen can lead to reactive molecules, such as hydroperoxides, 1, 2-dioxetanes and
endoperoxides. These compounds are useful for subsequent transformations, e.g., the ring
structure of cholesterol can add a peroxy group.
3.3.5. Photohydration
Uracil can add a molecule of water to it 5-6 double bond when UV irradiated.
79
great interest for such studies, because one can utilize red light or IR radiation, which is not
absorbed by biomolecules, and is biologically benign.
Rearrangements of electronically excited molecules present one of the most exciting chapters
in photochemistry in the sense that they follow reaction pathways that are usually
inaccessible for the ground state (activation barriers in the ground state are very high). The
cis-trans isomerization of double bonds belongs to such reactions. The azobenzene reaction
provides an instructive example. Scheme 1 shows photoinduced rearrangements of stilbene
that has been extensively studied. In addition to double bond isomerization, cis-stilbene
undergoes also cyclization with a lower quantum yield to form dihydrophenanthrene. The cis-
trans isomerization of stilbene occurs through rotation around the double bond. In the ground
state this rotation encounters a large barrier, i.e., there is a maximum on the ground-state
potential energy surface at the geometry corresponding to a twist angle of about 90o. In
contrast, both the first singlet excited state and triplet state have a minimum approximately at
the same geometry. The close proximity of the minimum and maximum facilitates a jump to
the ground state. The cis-trans isomerization of azobenzene may proceeds not only through
rotation, but also through nitrogen inversion, i.e. in-plane motion of the phenyl ring.
Scheme 1
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3.3.7. Photorearrangement
Two illuminating examples of photoinduced rearrangements of substituted benzaldehydes are
presented in Scheme 2. Intramolecular hydrogen transfer in 2-hydroxybenzaldehyde is an
extremely fast reaction in the singlet excited state. However, the process is completely
reversed upon a jump to the ground state. Overall, no chemical conversion is observed and
excitation energy is either dissipated as heat or emitted as light, but with a longer wavelength.
This behavior is typical for aromatic carbonyl compounds with ortho-hydroxy groups, and
they found application as UV protectors, in sunscreens for example. Molecules acting as UV
protectors absorb light that is harmful for biological molecules, and convert light into heat or
radiation that is biologically benign. In contrast, an intramolecular hydrogen transfer in 2-
nitrobenzaldehyde initiates a sequence of the ground-state reactions that leads to 2-
nitrosobenzoic acid. The latter molecule is a moderately strong acid, and dissociates in
aqueous solutions so that the photochemistry of 2-nitrobenzaldehyde can be used to create a
rapid pH-jump in solution. Many biological macromolecules, such as proteins and nucleic
acids, show pH-dependent conformational changes. Those changes can be monitored in real
time by using the light-induced pH-jump.
Scheme 2
Another important example is the conversion of 7-dehydrocholesterol to vitamin D3.
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3.3.8. Energy Transfer (Photosensitization)
When a second molecule is located near an electronically excited molecule, the excitation can
be transferred from one to the other through space. If the second molecule is chemically
different, there can be a substantial change in the luminescence. For example, the chemi-
luminescence of a jellyfish is actually blue, but, because the energy is transferred to GFP, the
observed fluorescence is green.
Photosensitized molecular oxygen is a powerfully oxidative species that severely hampers the
photosynthetic efficiency of plants and causes health problems such as cataracts in humans.
The ground state of molecular oxygen is very unusual in that it is a triplet; hence, it can
accept electronic energy from more-energetic triplet states of other molecules in a process
called quenching (as in the case of the space shuttle wing described above). When this
occurs, the donor molecule begins in its triplet state and undergoes a change in spin to its
singlet ground state. The molecular oxygen begins in its triplet ground state and also changes
spin to a singlet excited state. Because the total spin between the two molecules is
unchanged, the transfer of energy can occur rapidly and efficiently. The resulting molecular
oxygen singlet state phosphoresces in the far red and the near infrared. Moreover, it is both a
strong oxidant and peroxidant and, if formed, may chemically attack (oxidize) a nearby
molecule, often the same molecule that sensitized the molecular oxygen. The oxidation
reaction often changes the molecule to a form without colour. This light-induced bleaching
(one kind of photodamage) can be observed in nearly any coloured material left in sunlight.
In fact, the photosynthetic systems in plants must be continuously dismantled, repaired, and
rebuilt because of photodamage (primarily from singlet molecular oxygen).
Since the oxygen has an unpaired electron, it behaves in much the same way as an alkoxy
radical. Hydrogen abstraction and addition to double bonds are typical reactions. Cleavage of
neighboring carbon-carbon bonds may also occur, the two most common of these being
designated Type I and Type II.
An important primary photoprocess of carbonyl compounds is cleavage, also known as a
Norrish Type I reaction (Scheme 3). Besides recombination, the acyl and the alkyl radicals
formed in the primary reaction can undergo numerous secondary reactions that are
responsible for the multitude of final products.
82
Scheme 3
Scheme 4
4.0. SUMMARY
In this unit you have learnt that photochemical reactions are chemical reactions initiated by
the absorption of energy in the form of light. They involve electronic reorganization initiated
by electromagnetic radiation. The consequence of molecules absorbing light is the creation of
transient excited states whose chemical and physical properties differ greatly from the
original molecules. These new chemical species can fall apart, change to new structures,
combine with each other or other molecules, or transfer electrons, hydrogen atoms, protons,
or their electronic excitation energy to other molecules. Excited states are stronger acids and
stronger reductants than the original ground states. It is this last property that is crucial in the
most important of all photochemical processes, photosynthesis, upon which almost all life on
earth depends. What you have learned in this unit concerns the chemistry that distinguishes
photochemical reactions from other reactions. It has served to introduce you to the peculiar
types of photochemical reactions such as photo-isomerization, photo-oxidation, photo-
fragmentation, photo-rearrangement and photosensitization.
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5.0. TUTOR-MARKED ASSIGNMENT
(1) A photochemical reaction occurs when internal conversion and relaxation of an excited
state leads to a ground state isomer of the initial substrate molecule. Illustrate this with
stilbene.
(2) Explain how solvent viscosity affects the outcome of a photochemical reaction.
6.0. REFERENCES
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MODULE TWO
PERICYCLIC REACTION
1.0. INTRODUCTION
For the synthetic organic chemist, the development of a general procedure that leads to the
formation of carbon-carbon bonds is considered a laudable achievement. A general method
that results in the simultaneous formation of two carbon-carbon bonds is worthy of a Nobel
Prize. In 1950, two chemists, Otto Diels and Kurt Alder, received that accolade for their
discovery of a general method of preparing cyclohexene derivatives that is now known as the
Diels-Alder reaction. The Diels-Alder reaction is one type of a broader class of reactions that
are known as pericyclic reactions. Pericyclic reactions are the concerted reactions involving
reorganization of electrons which occur by the way of a single cyclic transition state.
Pericyclic reactions represent an important class of concerted (single step) processes
involving π-systems. The fact that the reactions are concerted gives fine stereochemical
control of the product; however, this module is more concerned with the general types of
pericyclic reaction, than with regio and stereochemical control. In 1965 two other Nobel
laureates, Robert B.Woodward and Roald Hoffmann, published a series of short
communications in which they presented a theoretical basis for these well known, but poorly
understood pericyclic reactions. Their theory is called orbital symmetry theory. Subsequently
other chemists published alternative interpretations of pericyclic reactions, one called frontier
orbital theory, and another named aromatic transition state theory. All of these theories are
based upon MO theory. In this module we will use the Diels-Alder reaction to illustrate
aspects of each of these theories.
Pericyclic reactions that involve a redistribution of bonding and non-bonding electrons in a
cyclic, concerted manner are an important class of organic reactions. Since the publications
of the Woodward-Hoffmann rules on the conservation of orbital symmetry and the frontier
molecular orbital theory (FMO) by Fukui first described in the late 1960s, the underlying
principles of these processes at the molecular level have become fully understood. Many
modern organic chemistry textbooks include pericyclic reactions as a major topic. They are
usually covered in detail in a typical introductory organic chemistry course. Among the two
fundamental approaches to pericyclic reactions, the FMO approach has gained some
popularity at the undergraduate teaching level. It is simpler and can be based on a pictorial
approach. A detailed understanding of molecular orbital theories and symmetry is not
required.
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Pericyclic reactions are popular with synthetic chemists because the reagents and conditions
are mild and the reactions are usually very "clean" unlike so many organic chemical reactions
that result in the formation of large quantities of brown-black, smelly by-product of unknown
composition.
2.0. OBJECTIVES
Reactions that proceed by nearly simultaneous reorganization of bonding electron pairs by way of
cyclic transition states have been termed pericyclic reactions. A pericyclic reaction is
characterized as a change in bonding relationships that takes place as a continuous, concerted
reorganization of electrons. The term "concerted" specifies that there is one single transition
state and therefore no intermediates are involved in the process. To maintain continuous
electron flow, pericyclic reactions occur through cyclic transition states. The cyclic transition
state must correspond to an arrangement of the participating orbitals which has to maintain a
bonding interaction between the reaction components throughout the course of the reaction.
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4. No ionic, free radical or other discernible intermediates lie on the reaction path.
5. The configuration of the product depends on: (i) the configuration of reactants (ii) The
number of electron pairs undergoing reorganization and (iii) the reaction conditions (like
thermal or photochemical).
Suprarafacial Antarafacial
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Figure 1: Suprafacial and Antarafacial Interactions
A different notation for configurational change is required for electrocyclic reactions. In these
cases a σ-bond between the ends of a conjugated π-electron system is either made or broken with
a corresponding loss or gain of a π-bond. For this to happen, the terminal carbon atoms of the
conjugated π- electron system must be rehybridized with an accompanying rotation or twisting of
roughly 900. The lobes of like sign can be either on the same side or on opposite sides of the
molecule. For a bond to form, the outermost pi lobes must rotate so that favorable bonding
interaction is achieved. If lobes of like sign are on opposite sides of the molecule: both orbitals
must rotate in the same direction, clockwise or counterclockwise .Woodward called this motion
conrotatory .That is, when viewed along the axis of rotation, the two end groups may turn in the
same direction, termed conrotatory. If two lobes of like sign are on the same side of the
molecule, the two orbitals must rotate in opposite directions-one clockwise and one
counterclockwise .Woodward called this a disrotatory opening or closure. When viewed along the
axis of rotation, the two end groups may turn in the opposite directions, termed disrotatory. The
prefixes con and dis may be remembered by association with their presence in the words concur
& disagree. These two modes electrocyclic reaction are shown in the diagram in the general form
in which they are most commonly observed. To form the new σ-bond in the electrocyclic
reaction, the p orbitals at the end of the conjugated system must overlap head-to-head.
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Figure 2: Conrotatory and Disrotatory twisting
Migration of a group across the same face of the pi system is a suprafacial rearrangement
Migration of a group from one face of the pi system to the other face is called an antarafacial
rearrangement
3.3.2 Cycloadditions Two or more molecules or molecular components (from now on,
“components”) react together to form two or more bonds in a new ring. It should be noted for
a sense of completeness that not all cycloadditions are pericyclic, and that they can occur in a
stepwise manner. This allows the selection rules to be broken (i.e. [2+2] additions etc. can
occur). The reactions can be made stepwise by equipping one reagent with a powerful
electron-donating group (nucleophilic) and the other with a powerful electron withdrawing
group (electrophilic). In assigning a cycloaddition to a class we assign descriptors π-, σ- or ω-
to the electrons directly involved in the process (i.e. those that move when curly arrows are
drawn), count how many electrons are involved in each component, and identify whether the
components are reacting in suprafacial (s) or antarafacial (a) modes.
3.3.3 Forbidden reactions and allowed reactions Not all cycloaddition reactions are
allowed. For example, [2+2] reactions are not. This is due to a kinetic barrier to reaction (2
alkenes forming a 4 membered ring is thermodynamically favourable, but kinetically
impossible). A “forbidden” reaction is expected to have an electronic barrier on the reaction
pathway due to unfavorable orbital properties. An “allowed” reaction is not expected to have
such a barrier. These terms are perhaps overly dramatic, but they indicate accurately the
tendencies of certain reactions to occur or not to occur. Generally, a thermal pericyclic
reaction is allowed if the number of electrons involved can be expressed as 4n+2. 4n is
forbidden. Crudely, an odd number of curly arrows is allowed while an even number is
forbidden. Conversely, photochemical pericyclic reactions are allowed if the number of
electrons is 4n, but not if it is 4n+2. Note though that when putting that much energy into a
reaction, other mechanisms may take precedence.
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4.0 SUMMARY
In this unit you have learned that a pericyclic reaction is a chemical reaction in which
concerted reorganization of bonding takes place throughout a cyclic array of continuously
bonded atoms. It may be viewed as a reaction proceeding through a fully conjugated cyclic
transition state. The number of atoms in the cyclic array is usually six, but other numbers are
also possible. The term embraces a variety of processes, including cycloadditions, cheletropic
reactions, electrocyclic reactions and sigmatropic rearrangements (provided they are
concerted). Concerted means that all bonding changes occur at the same time and in a single
step (no intermediates).
2. (a) What do the following acronyms stand for (i) HOMO (ii) LUMO (iii) SOMO?
6.0 REFERENCES
1.Woodward, R.B.; Hoffmann, R. The Conservation of Orbital Symmetry, 2004, Verlag
Chemie Academic Press.
2 .Barltrop, J.A., Coyl, J.D. Excited states in organic chemistry, 1975, London; New York:
Wiley.
3. Pericyclic reaction - Wikipedia, the free encyclopedia
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UNIT 2 - TYPES OF PERICYCLIC REACTIONS
1.0 INTRODUCTION
More simply, the term “pericyclic” covers all concerted reactions involving a cyclic flow of
electrons through a single transition state. While in this transition state, a concerted
rearrangement of the electrons takes place which causes sigma and π- bonds to
simultaneously break and form. Pericyclic reactions can be predicted and controlled to a great
degree, which makes them very useful in synthesis. Pericyclic reactions are popular with
synthetic chemists because the reagents and conditions are mild and the reactions are very
"clean"... unlike so many organic chemical reactions that result in the formation of large
quantities of brown-black, smelly by-product of unknown composition. Pericyclic reactivity
can be understood in terms of frontier molecular orbital (FMO) theory and the outcome of
reactions can be predicted using the Woodward-Hoffmann rules.
2.0 OBJECTIVES
At the end of this Unit, you should be able to:
• Explain the major categories of pericyclic reactions
• Give appropriate examples of each category of pericyclic reactions
• Compare different types of pericyclic reactions
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Cycloaddition reactions involve the formation of a cyclic product due to addition of two
different π bond containing components, which are joined by newly formed two σ bonds at
their ends at the expense of two π bonds. It is usually reversible and the backward reaction is
also referred to as retro-cycloaddition or a cycloreversion. The classic example of
cycloaddition is Diels-Alder reaction between a Diene and a Dienophile to give a cyclic
adduct. Cycloaddition, and the reverse process retrocycloaddion, can be observed in the
reaction between 1,3-butadiene and ethene to give cyclohexene.
That is:
The 1,3-butadiene is a conjugated π-system with 4 π-electrons and the ethene is a conjugated
π-system with 2 π-electrons. The reaction between 1,3-butadiene and ethene to give
cyclohexene is described as a [4+2] cycloaddition reaction. This type of cycloaddition is also
called a Diels-Alder reaction. In a Diels-Alder reaction the 4 π-electron system is referred to
as "the diene" and the 2 π-electron system as the "dieneophile". These terms are used in
related [4+2] reaction systems even when the functional groups are not actually dienes or
alkenes.
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However, many cycloaddition reactions require moderate heating to overcome the activation
energy. So a cycloaddition may require heating to make the reaction "go", but if it is heated
too much the equilibrium will favour retrocycloaddition. The compound cyclopentadiene
slowly undergoes cycloaddition with itself: one molecule of cyclopentadiene acts as a 4 π-
electron diene and the other as a 2 π-electron dieneophile. The product is a Diels-Alder
"adduct", often called dicyclopentadiene. This dimeric material can be cracked back to
cyclopentadiene by heating at 150°C for an hour and then distilling off the diene monomer.
Diels-Alder cycloaddition reactions proceed more efficiently if the diene is electron rich and
the dienophile is electron poor. Cyclopentadiene is electron rich. The way to make the
dieneophile electron poor is to add electron withdrawing groups, such as carbonyl functions.
Maleic anhydride is an electron poor dieneophile which reacts with cyclopentadiene to give
an endo Diels-Alder adduct. Upon heating at 190°C, the endo conformation adduct adopts the
more stable exo-adduct conformation.
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3.3 Cheletropic reactions
These are a special class of cycloadditions or retro-cycloadditions in which the two σ-bonds
are either made or broken to the same atom. For example, the reversible addition of sulfur
dioxide to 1,3-butadiene is an example of cheletropic reaction, in which the two new σ-bonds
are made to the sulfur atom.
Note: In this reaction, a lone pair on sulfur atom is equivalent a π-bond and is reorganized.
One π-bond and a lone pair are disappeared, whereas two σ-bonds are formed. Also note that
sulfur atom is oxidized from +4 to +6 state.
That is:
Note that the 3-alkene must be cis for the reaction to occur.
The reverse, or retroelectrocyclic, reaction can also occur. This is seen with the ring opening
of cyclobutene to 1,3-butadiene:
Electrocyclic reactions, like all pericyclic processes, exhibit great stereoselectivity. Consider
two 1,3,5-hexatriene systems embedded into longer hydrocarbon chains.
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trans-cis-trans-2,4,6-Octatriene will ring-close to give a cis ring:
Note: Though looking like electrocyclic reactions, there is no reduction in the number of π-
bonds in sigmatropic reactions.
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The [3,3] Cope rearrangement:
Note that the generic "R" functions have been added so that the product can be distinguished
from the starting materials.
The biosynthesis of vitamin D has photochemical step, and the reaction takes place in skin
cells. A 1,3-cyclohexadiene system associated with the b ring of a steroid undergoes a
photoactivated, retroelectrocyclisation to give 1,3,5-hexatriene system. The thermal reaction
is not allowed because it would be necessary to form a six membered ring with a trans-
alkene, a sterically impossible structure. 1,3,5-hexatriene system then undergoes a thermal
[1,7] sigmatropic rearrangement to give vitamin D3. This is further processed in the liver.
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Figure 1 Sigmatropic rearrangement in biosynthesis of vitamin D
The [3,3] sigmatropic rearrangement of 1,5-dienes or allyl vinyl ethers, known respectively as the
Cope and Claisen rearrangements, are among the most commonly used sigmatropic reactions.
Three examples of the Cope rearrangement are shown in the following diagram. Reactions 1 and
2 demonstrate the stereospecificity of this reaction. Since each allyl segment is the locus of a
[1,3] shift, the overall reaction is classified as a [3,3] rearrangement. The three curved arrows
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describe the redistribution of three bonding electron pairs in the course of this reversible
rearrangement. The diene reactant in the third reaction is drawn in an extended conformation.
The concerted transfer of a group from one molecule to another due to concomitant
movement of a σ-bond (from one molecule to another) and formation of a new σ-bond
(between two molecules) at the expense of a π-bond is generally referred to as group
transfer pericyclic reaction. For example, the ene reaction between propene and ethene to
give 1-pentene is a classic example of group transfer reaction.
Another example of an ene reaction is seen with the reaction of methylenecyclohexene and
methyl acrylate. (An aluminium chloride catalyst is required to "activate" the enone system.)
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The reaction proceeds as a retroene reaction to give carbon dioxide and an enol system. The
loss of CO2 drives the reaction to the right hand side. The enol rapidly tautomerises to the
methyl ketone:
Diimide is used as a reducing agent, it adds H2 to C=C and N=N bonds and leaves other
functions untouched:
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3.7 Dyotropic rearrangements
The pericyclic reactions which involve concerted intramolecular migration of two σ-bonds
simultaneously are known as dyotropic rearrangements. However dyotropic reactions can
also occur stepwise. There are two types of dyotropic rearrangements:
Type-II: The σ-bonds are migrated to new bonding sites without any positional interchange
for groups.
All types of pericyclic reactions are concerted and involve cyclic transition state without any
intermediate formed during the reaction. The characteristics which differentiate them from
each other are tabulated below.
change in change in
Type of pericyclic
S.no no. of no. of comments
reaction
σ bonds π bonds
Electrocyclic
2) +1 -1 Intramolecular.
reactions
Intramolecular;
Sigmatropic
3) 0 0 migration of a σ-bond;
reactions
rearrangement of π-electrons
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A cyclic product is formed;
-1 (π-bond)
Cheletropic two σ-bonds are formed to same
5) +2 -1 (lone
reactions atom;
pair)
A lone pair is disappeared.
4.0 SUMMARY
6.0 REFERENCES
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UNIT 3-ANALYSIS OF PERICYCLIC REACTIONS
1.0 INTRODUCTION
The Diels-Alder reaction is one type of a broader class of reactions that are known as
pericyclic reactions. In 1965 two other Nobel laureates, Robert B.Woodward and Roald
Hoffmann, published a series of short communications in which they presented a theoretical
basis for these well known, but poorly understood pericyclic reactions. Their theory is called
orbital symmetry theory. Subsequently other chemists published alternative interpretations of
pericyclic reactions, one called frontier orbital theory, and another named aromatic transition
state theory. All of these theories are based upon MO theory. In this unit we will use the
Diels-Alder reaction to illustrate aspects of each of these theories.
2.0 OBJECTIVES
At the end of this Unit you should be able to:
• Analyze pericyclic reactions using the orbital correlation diagram method, the frontier
molecular orbital (FMO) approach.
• Give the reaction conditions for pericyclic reactions
• Use Woodward-Hoffmann rules to predict allowed pericyclic reaction
1. Bonding orbitals undergoing significant change in the reaction, and their antibonding
counterparts, should be identified.
2. If polyene moieties are involved, all the molecular orbitals of that conjugated system must be
used.
3. Ignoring non-participating substituents and heteroatoms, the symmetry elements of the
essential molecular skeleton must be identified. All orbitals not clearly symmetric or
antisymmetric with respect to these molecular symmetry elements need to be mixed or until they
become so. In the construction of the orbital correlation diagram caution is exercised in choosing
the symmetry elements.In this respect, the only important symmetry elements are those that bisect
bonds that are made or broken in the reaction. Mixing is usually required for σ orbital analysis.
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4. Each bonding and antibonding orbital included in the correlation is assigned one or more
symmetry designations, S for symmetric, A for antisymmetric, depending on its fit with each
characteristic symmetry element
5. The molecular orbitals are then arrayed according to their energy (increasing vertically), and
location on the reaction coordinate (horizontally). Correlations of reactant and product orbitals
are drawn so that orbitals of like symmetry are connected.
3.3 Orbital symmetry diagram (Orbital correlation diagram)
3.3.1 Conservation of Orbital Symmetry Theory: Explains the relationship among the
structure and configuration of the reactant, the conditions (thermal or photochemical) under
which the reaction takes place, and the configuration of the products. In 1965 R. B. Woodward
and Roald Hoffmann of Harvard University proposed and demonstrated orbital symmetry rule,
states that in-phase orbitals overlap during the course of a pericyclic reaction. Concerted reactions
proceed most readily when there is congruence between the orbital symmetries of the reactants
and products. In other words, when the bonding character of all occupied molecular orbitals is
preserved at all stages of a concerted molecular reorganization, that reaction will most likely take
place. The greater the degree of bonding found in the transition state for the reaction, the lower
will be its activation energy and the greater will be the reaction rate. A symmetry-allowed
pathway is one in which in-phase orbitals overlap. If a reaction is symmetry-forbidden, it cannot
take place by a concerted pathway. If the symmetries of both reactant and product orbitals match
the reaction is said to be symmetry allowed under the Woodward-Hoffmann Rules. If the
symmetries of reactant and product orbitals do not correlate, the reaction is symmetry-disallowed
and there are no low energy concerted paths.
The fundamental feature of the orbital symmetry analysis is to draw the MOs of the
reactant(s) and the MOs of the product(s). One then considers how the symmetries of the
orbitals relate to each other. Orbitals of reactants are transformed smoothly into orbitals of
products, with conservation of orbital symmetry.
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3.3.2 Analysis of cycloaddition reaction by orbital correlation diagram method
Consider the [2+2] cycloaddition of two ethylene molecules. Let us assume that the two
molecules approach each other with their π systems arranged symmetrically (i.e., a symmetric
pericyclic transition state). If so, then we can identify two symmetry elements: two mirror
planes, as shown. Each pair of interacting pi orbitals in the reactant combination leads to one
σ bond in the cyclobutane product.
Figure 2 defines the conditions implied by the term head-to-head, namely that the reactants
approach each other in parallel planes with the pi orbitals overlapping in the head-to-head
fashion required for the formation of sigma bonds. The sigma-bonded atoms of each ethene
lie in the two parallel planes shown in black in the figure. The p orbitals on each carbon lie in
the vertical plane which is shown in blue. The two planes shown in red are symmetry planes.
Plane 1 bisects the C-C bond of each ethene, while plane 2 lies half way between the two
planes shown in black.
According to the conventions of orbital symmetry theory, the reaction shown in Figure 2 is
classified as a π2s + π2s cycloaddition, where π indicates that the reaction involves a π
system, the number 2 is the number of electrons in the reacting π system, and the letter s
stands for suprafacial: if one lobe of a p orbital is considered as the top face, while the other
lobe is called the bottom face, then a suprafacial interaction is one in which the bonding
occurs on the same face at both ends of the π system. The orientation of the interacting ¼
systems depicted in Figure 2 implies something about the stereochemical outcome of the
reaction. Consider the π2s + π2s cycloaddition shown in Equation 3, where the two new
sigma bonds are shown in red.
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Because the interacting π systems approach each other in a "head-to-head" fashion, the
relative stereochemistry is the same in the products as it is in the reactants, i.e. the two
carboxyl groups that are "cis" to each other in the alkene are "cis" to each other in the
products.
Example 1: Interconversion of cyclobutene to butadiene. For the disrotatory process not all
the orbitals correlate with ground state orbitals of butadiene. The following conclusions can
be drawn from the correlation diagram.
1. We expect a thermal transformation to take place only when the ground state orbitals of
cyclobutene correlate with the ground state orbitals of butadiene. Even though σ correlates
with π1, the π orbital of cyclobutene is not correlating with π2 of butadiene. Thus thermal
transformation of cyclobutene to butadiene by disrotatory process is symmetry forbidden.
2. Irradiation of cyclobutene causes excitation with electron distribution σ2, π1, π*1, which
correlates with first excited state orbitals of butadiene. The photochemical process is
symmetry allowed.
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Eample 2: Conrotaory ring opening of cyclobutene –butadiene –C2 symmetry. From the
correlation diagram two conclusions can be drawn:
1. since there are correlation between the ground state orbitals of cyclobutene and butadiene.
Similarly the first excited state of butadiene is correlating with a higher energy upper excited
state of cyclobutene .i.e., a photochemical conrotatory process in either direction is symmetry
forbidden.
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On similar grounds we can work out the disrotatory and conrotatory modes interconversion of
hexatriene – cyclohexadiene. It can be noted that the thermal disrotatory and photochemical
conrotatory processes are symmetry allowed.
These generalizations are Woodward –Hoffmann rules for electro cyclic reactions which can be
summarized as
Frontier Molecular Orbital Theory was developed in the 1960s by Kenichi Fukui who
recognized that chemical reactivity can often be explained in terms of interacting Highest
Occupied MOs (HOMOs), Lowest Unoccupied MOs (LUMOs) and Singly Occupied MOs
(SOMOs).
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• LUMO + LUMO -> null interaction (no electrons)
• SOMO + SOMO -> bonding MO
The FMO approach was developed by Woodward & Hoffmann in the late nineteen sixties
who used it to explain an apparently diverse set of reactions involving π-systems, including
Diels-Alder cycloaddition. Hoffmann used the approach to explore transition metal
complexes.
Cycloaddition can be explained using frontier molecular orbital (FMO) theory. The alkene
(dienophile) component has two electrons is a "single" π-bond. FMO theory, here, identifies
the HOMO and LUMO components of this system:
Likewise, the diene which has four electrons in its conjugated π-system can have its HOMO
and LUMO identified within FMO theory:
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Figure 4: HOMO/LUMO components of a diene
If we examine the phases at the ends (termini) of the diene and dieneophile we find that the
LUMO/HOMO interactions are phase matched:
Notice that the phases match whichever species is defined as the HOMO or LUMO. In
reality, the electron rich species reacts via its HOMO and the electron poor species via its
LUMO.
In the FMO diagrams above, the sizes or coefficients are all the same size, but usually they
are of different sizes. The rule is that the coefficients match as well: small with small and
large with large:
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Figure 6: Coefficient and phase matched HOMO/LUMO
We can use Hückel MO theory to calculate the sizes of the coefficients at each of the atoms.
(There is a web based HMO calculator, here, although at meta-synthesis we use a stand alone
package: HMO by Allan Wissner.)
If the coefficients are calculated for 1-methoxy-1,3-butadiene the termini are +0.3 and –0.58
(or –0.3 and and +0.58). For acrylonitrile the coefficients are +0.2 and –0.66 (or –0.2 and
+0.66).
The cycloaddition reaction proceeds so the coefficients "match", both in in terms of phase
(essential) and in terms of coefficient magnitude: +0.3 with +0.2 and –0.58 with –0.66.
Fukui realized that a good approximation for reactivity could be found by looking at the
frontier orbitals (HOMO/LUMO). This was based on three main observations of molecular
orbital theory as two molecules interact:
From these observations, frontier molecular orbital (FMO) theory simplifies reactivity to
interactions between the HOMO of one species and the LUMO of the other. This helps to
explain the predictions of the Woodward–Hoffmann rules for thermal pericyclic reactions,
which are summarized in the following statement:
"A ground-state pericyclic change is symmetry-allowed when the total number of (4q+2)s and
(4r)a components is odd"
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(4q+2)s refers to the number of aromatic, suprafacial electron systems; likewise, (4r)a refers
to antiaromatic, antarafacial systems. It can be shown that if the total number of these
systems is odd then the reaction is thermally allowed.
Electrocyclic reactions, like all pericyclic processes, exhibit great stereoselectivity. Consider
two 1,3,5-hexatriene systems embedded into longer hydrocarbon chains.
As with cycloaddition, this selectivity can be explained by examining the FMOs, specifically
the HOMO:
111
Figure 7: Superimposition of HOMO upon triene system
If the termini of the HOMO are superimposed upon the triene system, it can be seen that the
end groups must rotate in a disrotatory manner (twist in opposite directions, when viewed
front-on) to form the bond:
The photoexcited system will ring-close in the opposite manner to the thermal system and the
groups conrotate (twist the same way) to form the sigma bond:
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Figure 9: Conrotation of photoexcited System
This thermal and photo selectivity can be exploited in the reaction sequence below in which
1,3,5-cyclononatriene is converted into bicyclic systems, first with cis and then trans ring
junctions.
The initial 1,3,5-cyclononatriene is all cis. This is thermally ring closed in a disrotatory
manner and then photo-ring opened at -20°C in a conrotatory manner. The 1,3,5-
cyclononatriene now has two cis and one trans double bonds, however, the nine membered
ring is able to accommodate the strain of a trans alkene. Thermal ring closure gives the trans-
ring junction.
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Figure 10 Conrotatory twist of 1,3,5-cyclononatriene
It is observed that some of the pericyclic reactions occur only upon heating, whereas others
are possible only under photochemical conditions e.g. the Diels-Alder reaction, a [4+2]
cycloaddition occurs under thermochemical conditions and is not possible under
photochemical conditions.
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Whereas the following [2+2] cycloaddition is forbidden under thermal conditions. But the
reaction is possible under photochemical conditions.
To predict whether a pericyclic reaction is allowed or not under given condition, Woodward
and Hoffmann proposed following set of rules Woodward-Hoffmann rules concept.
A thermal pericyclic reaction is allowed in the ground state, when the total number of (4q +
2)s and (4r)a components is odd.Otherwise, if the total of (4q + 2)s and (4r)a components is
even, the pericyclic reaction is allowed in the excited state i.e., under photochemical
conditions.
Number of (4q + 2)s and (4r)a components The condition under which the reaction is
allowed
odd Thermal
even Photochemical
Component: A bond(s) or an orbital(s) taking part in the pericyclic reaction as a single unit
can be considered as a component. It can have any number of electrons but may not have
mixtures of π and σ electrons. E.g. A double bond is considered as a π2 component, since
there are two π electrons. A conjugated diene can be considered as π4 component, since there
are four π electrons. 's' represents suprafacial. A suprafacial component forms new bonds on
the same face at its both ends. 'a' represents antarafacial. An antarafacial component forms
new bonds on the opposite faces of its both ends. E.g. π2s represents a component containing
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two π electrons and forming new bonds in suprafacial manner. π4a represents a component
containing four π electrons and is going to form new bonds in antarafacial manner.
(4q + 2)s component: The suprafacial component which may have either 2 or 6 or 10 or _ _ _
electrons of same type. These numbers are obtained by substituting 'q' by 0 or 1 or 2 or _ _ _.
Application: Let us assume the diene and dienophile in Diels-Alder reaction are
approaching suprafacially as shown below.
Since there are 4 π electrons in diene, which is making bonds in suprafacial manner it is a (4q
+ 2)s component. i.e, there is one (4q + 2)s component. And the alkene is a (4r)s component,
since it has 2 π electrons and is approaching the diene suparfacially i.e., there are no (4r)a
components. Hence, the total number of (4q + 2)s and (4r)a components = 1 + 0 = 1, an odd
number. Therefore Diels-Alder reaction is thermally allowed in ground state when both the
components are approaching suprafacially. Hence it is termed as π4s + π2s cycloaddition.
Antarafacial addition is not allowed under thermal conditions but is theoretically allowed
under photochemical conditions in the excited state. However, the strain in the transition state
while doing so forbids to do so.
Note: The orbitals shown in above diagrams are simple 'p' orbitals and are not the frontier
molecular orbitals. Do not mix descriptions of FMO theory with Woodward-Hoffmann rules.
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3.6.1 Simplified Woodward-Hoffmann rules
Remember that even though the pericyclic reactions are allowed theoretically under both the
conditions in either of the modes, sometimes the factors like steric hindrance and strain in the
transition state may forbid the reaction to occur.
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Before we move on, it is worthwhile to clarify the implications of the words allowed and
forbidden. An allowed reaction is simply one with a low activation relative to some other
pathway, while a forbidden reaction is a process for which there is significant activation
energy. In terms of transition states, an allowed reaction proceeds via an aromatic transition
state, while a forbidden reaction does not occur because the transition state would be "anti-
aromatic."
4.0 SUMMARY
In this unit you have learnt the various rules of pericyclic reactions. All of the theories just
described involve two basic assumptions
These rules are summarized in Table 4.4. Note that changing just one of the variables, i.e.
faciality, energy source, or number of electrons (two electrons at a time), changes an allowed
reaction to a forbidden one and vice versa. Below are some other fine points:
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5.0 TUTOR-MARKED ASSIGNMENTS
6.0 REFERENCES
3. Woodward, R. B., Hoffmann, R. (1971). The Conservation of Orbital Symmetry;
Academic Press: New York
4. Barltrop, J.A., Coyl, J.D. (1975) Excited states in organic chemistry. London ; New
York: Wiley.
6). Phototropism.
7).Pericyclic reactions are concerted and involve cyclic transition state without any
intermediate formed during the reaction.
8). Three types of pericyclic reactions: 1) electrocyclic, 2) cycloaddition, 3) sigmatropic
rearrangement.
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