Lecture 27

Chemical characterization by spectroscopic techniques

27.1 Introduction
Electromagnetic radiation (light) is a form of energy whose behaviour is described by the
properties of both waves and particles. Some properties of electromagnetic radiation, such as
its refraction when it passes from one medium to another, are explained best by describing
light as a wave. Other properties, such as absorption and emission, are better described by
treating light as a particle.
Electromagnetic radiation consists of oscillating electric and magnetic fields that
propagate through space along a linear path and with a constant velocity. In a vacuum
electromagnetic radiation travels at the speed of light. When electromagnetic radiation moves
through a medium other than a vacuum its velocity, v, is less than the speed of light in a
vacuum.
When matter absorbs electromagnetic radiation it undergoes a change in energy. The
interaction between matter and electromagnetic radiation is easiest to understand if we
assume that radiation consists of a beam of energetic particles called photons. When a photon
is absorbed by a sample it is “destroyed,” and its energy acquired by the sample. The energy
of a photon, in joules, is related to its frequency, wavelength, and wavenumber by the
following equalities:

where h is Planck’s constant, which has a value of 6.626 × 10–34 J . s.

The frequency and wavelength of electromagnetic radiation vary over many orders
of magnitude. EM radiation into different regions—the electromagnetic spectrum—based
on the type of atomic or molecular transition that gives rise to the absorption or emission of
photons. The boundaries between the regions of the electromagnetic spectrum are not rigid,
and overlap between spectral regions is possible.

Fig. The electromagnetic spectrum

 Spectroscopy is the study of interaction between matter and radiated energy.
Example- analysis of white light through prism. Using spectroscopy, one measures the
radiation intensity as a function of wavelength and determine surface, interior atoms,
compounds and their spatial distribution.
Spectroscopy is used in physical and analytical chemistry because atoms and
molecules have unique spectra. These spectra can be used to detect, identify and quantify
information about atoms and molecules.

A spectrometer is an instrument for making relative measurements in the optical

spectral region, using light that is spectrally dispersed by means of a dispersing element. We
direct the light onto the sample. We know the intensity and wavelength of that light. Then we
use a detector of some sort to measure what comes out the other side. What we will see is a
spectrum. We see a change in the absorbance or intensity of that light as we move across the
spectrum and change the wavelength.
Based on these fundamentals, we have different spectroscopic techniques available to
us as scientists and engineers that can be broadly classified as:
A. Optical spectroscopy
B. Electron spectroscopy
C. Ion spectroscopy

27.2 Optical Spectroscopy

Optical spectroscopy is a means to study the properties of physical objects based on

measuring how an object emits and interacts with light. The technique can be categorized into
two groups:

a. Absorption and emission spectroscopy: determines the electronic structure of

atoms, ions, molecules or crystals through exciting electrons from the ground to
 excited states (absorption) and relaxing from excited to ground states (emission).
Absorption and photoluminescence spectroscopy fall into this category.
b. Vibrational spectroscopy: involve interactions of photons with species in the sample
that results in energy transfer to or from the sample via vibrational excitation or de-
excitation. The vibrational frequencies provide information of chemical bonds in the
detecting samples. Infra-red spectroscopy and raman spectroscopy fall into this
category.

27.2.1 Absorption and emission spectroscopy

Absorption spectroscopy refers to spectroscopic techniques that measure the absorption of
radiation, as a function of frequency or wavelength, due to its interaction with a sample. The
sample absorbs energy, i.e photons, from the radiating field and transition occurs from a
lower-energy state to a higher energy, or excited state. The intensity of the absorption varies
as a function of frequency, and this variation is the absorption spectrum.
When a photon of energy hν strikes the atom or molecule, absorption may occur if the
difference in energy, ΔE, between the ground state and the excited state is equal to the
photon’s energy. When it absorbs electromagnetic radiation the number of photons passing
through a sample decreases. The measurement of this decrease in photons, which we call
absorbance, is a useful analytical signal.
Note that the each of the energy levels has well-defined value because they are quantized.
Absorption occurs only when the photon’s energy, hν, matches the difference in energy, ΔE,
between two energy levels.
Fig. Simplified energy diagram showing the absorption and emission of a photon by an atom
or a molecule.

Absorption spectroscopy is employed as an analytical chemistry tool to determine the

presence of a particular substance in a sample and to quantify the amount of the substance
present.

27.2.1.1 Working Principle

A white beam source – emitting light of multiple wavelengths – is focused on a sample (the
complementary color pairs …….as yellow dotted lines). Upon striking the sample, photons
that match the energy gap of the molecules present (green light in this example) are absorbed
in order to excite the molecule. Other photons transmit unaffected and, if the radiation is in
the visible region (400-700nm), the sample color is the complementary color of the absorbed
light. By comparing the attenuation of the transmitted light with the incident, an absorption
spectrum can be obtained.
27.2.1.2 Absorption spectrum
A material's absorption spectrum is the fraction of incident radiation absorbed by the material
over a range of frequencies. The absorption spectrum is primarily determined by the atomic
and molecular composition of the material. Radiation is more likely to be absorbed at
frequencies that match the energy difference between two quantum mechanical states of the
molecules. The absorption that occurs due to a transition between two states is referred to as
an absorption line and a spectrum is typically composed of many lines. The frequencies
where absorption lines occur, as well as their relative intensities, primarily depend on the
electronic and molecular structure of the sample. The frequencies will also depend on the
interactions between molecules in the sample, the crystal structure in solids, and on several
environmental factors (e.g., temperature, pressure, electromagnetic field). The lines will also
have a width and shape that are primarily determined by the spectral density or the density of
states of the system.
A plot of absorbance as a function of the photon’s energy is called an absorbance spectrum.

Fig. Visible absorbance spectrum for cranberry juice. The anthocyanin dyes in cranberry
juice absorb visible light with blue, green, and yellow wavelengths. As a result, the juice
appears red.

27.2.2 Photoluminescence Spectroscopy

Photoluminescence (PL) is light emission from any form of matter after the absorption of
photons (electromagnetic radiation). It is one of many forms of luminescence (light emission)
and is initiated by photoexcitation (excitation by photons). Following excitation various
relaxation processes typically occur in which other photons are reradiated.
 Fig. (a–c) Radiative recombination paths: (a) band-toband; (b) donor to valence band; (c)
conduction band to acceptor (d) Nonradiative recombination via an intermediate state.

When an atom or molecule in an excited state returns to a lower energy state, the
excess energy often is released as a photon, a process we call emission. There are several
ways in which an atom or molecule may end up in an excited state, including thermal energy,
absorption of a photon, or by a chemical reaction. Emission following the absorption of
a photon is also called photoluminescence, and that following a chemical reaction is called
chemiluminescence.
Typically, light is directed onto the sample for excitation and the emitted
luminescence is collected by a lens and passed through an optical spectrometer onto a photon
detector.

Fig. Typical experimental set-up for PL measurements

The intensity and spectral content of the emitted photoluminescence is a direct

measure of various important material properties:
 i. Chemical composition
ii. Structure
iii. Impurities
iv. Kinetic process
v. Energy transfer
vi. Bandgap determination
vii. Defect detection
viii. Recombination mechanisms.

27.2.2.1 Working Principle

a. Material gains energy by absorbing photon at some wavelength (by promoting an electron
from a low to higher energy level).
b. The system then undergoes a non-radiative internal relaxation involving interaction with
crystalline/molecular vibrational and rotational modes.
c. The excited electron moves to a more stable excited level (as bottom of conduction band or
lowest vibrational molecular state).
d. After a characteristic lifetime in the excited state, electron return to the ground state.
e. Some of all the energy released during this final transition is in form of light (radiative) and
the wavelength of this emitted light is longer than that of the incident light.

Fig. Photoluminescence spectrum of the dye coumarin 343.

Lecture 28 Chemical characterization by spectroscopic
techniques (contd….)

28.1 Vibrational Spectroscopy

All matter contains molecules; these molecules have bonds that are continually vibrating
and moving around. These bonds can vibrate with stretch motions or bend motions.
Imagine two balls attached by a spring, representing a diatomic molecule. The movement
of each ball toward or away from the other ball along the line of the spring represents a
stretching vibration. Stretching can either be symmetric or asymmetric.

Fig. Stretching Vibrations

A molecule with three or more atoms can experience a bending vibration, a vibrational mode
where the angle between atoms changes.

Fig. Bending Vibrations

 Each excited vibrational state is reached when a molecule is exposed to a specific
frequency. In order for a bond to be promoted to the excited state, it must be exposed to
radiation of the exact same frequency as the energy difference between ground and excited
states (ΔE). Determining these frequencies and representing them allows us to determine the
bonds that exist in a molecule. These frequencies all lie within the infrared region of the
electromagnetic region, a region of lower wavelength than visible light.

28.2 Infrared Spectroscopy

As mentioned, infrared light matches the vibrational frequencies of the molecular bonds.
When infrared light is incident on the molecule, the frequency which corresponds with the
natural vibrational frequency may be absorbed by the molecule, increasing the magnitude of
the natural molecular vibrations. Some bonds absorb more strongly than others, and some
compounds give very complex spectra. The infrared region considered in this note is the mid-
infrared, from 4500cm-1 to 400 cm-1.
The frequencies and intensities of absorbed infrared light depend on the specific bond
strengths and atoms of that molecule, and the absorption pattern (called a spectrum) is unique
for each material. The condition of the material, such as the temperature, the state (solid,
liquid, or gas), concentration, pressure, and other materials in a mixture also affect the
spectrum. It is this spectrum that makes infrared spectroscopy a very powerful tool for both
qualitative and quantitative analysis.
In order for a vibration to be “infrared active”, it is necessary for a change in the
dipole moment to occur during the absorption of the infrared light. In other words, the
electronic charge distribution from one side of the bond to the other must occur. Consider
hydrogen chloride, HCl. When HCl vibrates along the bond, the chlorine takes on a slightly
more negative charge, and the hydrogen takes on a slightly more positive charge.
Consequently, a change in dipole moment of the HCl molecule occurs. In some molecules,
such as homonuclear diatomics (O2, N2, H2, F2, Cl2, Br2, I2) there is no induced dipole
moment, and these compounds are considered IR-inactive. Similarly, the noble gases (He,
Ne, Ar, Kr) and most vaporized elements (e.g. Hg) are monatomic and have no bonds at all.
These compounds are few and there are other techniques for measuring them.
IR spectra are acquired on a special instrument, called an IR spectrometer. The
infrared spectrum is measured by either absorbance or percent transmittance on the y-axis
and by either the wavelength (um) or wavenumber (cm-1) to measure the position of an
infrared absorption on the x-axis. Most compounds have characteristic absorptions in the
infrared region.
The vibrational spectrum of a molecule is considered to be a unique physical property
and is characteristic of the molecule. As such, the infrared spectrum can be used as a
fingerprint for identification by the comparison of the spectrum from an ‘‘unknown’’ with
previously recorded reference spectra.
A typical IR spectrum is shown below.

Fig. The IR spectrum of octane, plotted as transmission (left) and absorbance (right)

28.2.1 Application
a. The infrared spectrum is qualitatively useful in determining the identity of a
compound, as all materials have different infrared signatures.
b. The infrared spectrum is also quantitatively useful as the strength of the infrared
absorbances vary with concentration.
c. Gas phase measurements using infrared spectroscopy are especially powerful as
sample concentrations can be analyzed over 12 orders of magnitude, from parts-per-
billion levels up to pure materials where trace impurities are of interest.
d. IR spectroscopy is useful in determining chemical structure (identities, atomic
arrangement, concentration of chemical bonds) because energy that corresponds to
specific values allows us to identify various functional groups within a molecule.

28.3 Raman Spectroscopy

Raman spectroscopy provides key information about the structure of molecules. The position
and intensity of features in the spectrum reflect the molecular structure and can be used to
determine the chemical identity of the sample. Spectra may also show subtle changes
depending on the crystalline form. With the extensive spectral libraries that are now
available, it is very straight forward to identify compounds by spectral library searching.

Infrared and Raman spectroscopy are used as complementary techniques, because each
method looks at different aspects of a given sample. The physical method of observing the
vibrations in Raman is different from IR spectroscopy. In Raman spectroscopy, one measures
the scattering of photons, while IR spectroscopy is based on absorption of photons. IR is
sensitive to functional groups and to highly polar bonds, Raman is more sensitive to
backbone structures and symmetric bonds. Using both techniques provides twice the
information about the vibrational structure than can be obtained by using either alone. In
addition to providing unique information about a sample, Raman offers several additional
benefits, including:
• Minimal or no sample preparation
• Sampling directly through glass containers
• Non-destructive analysis, so the same sample can be used in other analyses
• Non-intrusive analysis, permitting study of more labile sample features, such as crystal
structure
• Minimal water interference
• No interference from atmospheric CO2 or H2O

The vibrational states probed by Raman spectroscopy are similar to those involved in
infrared spectroscopy. However, the two vibrational spectroscopy techniques are
complementary, in that vibrations that are strong in an infrared spectrum (those involving
strong dipole moments) are typically weak in a Raman spectrum. Likewise, non-polar
functional group vibrations that give very strong Raman bands usually result in weak infrared
signals.
 Fig. Raman Spectra: carbon tetra chloride

28.3.1 The Raman Effect

When a sample is irradiated with an intense monochromatic light source (usually a laser), the
electrons are excited to a virtual level. Since, a molecule cannot remain in this virtual level, it
must immediately fall back down to a lower level with the emission of a photon. If the
molecule falls into the same level as it started from, there is no frequency shift in the emitted
photon and there is Rayleigh scattering.
If, on the other hand, the molecule falls into a different level, the energy of the
emitted photon must differ (inelastic scattering) from that of the incoming photon in order to
conserve total energy. In this case, the emitted photon has a different frequency from that of
the initial photon. This process is called Raman scattering. The frequency can decrease
(giving rise to Stokes lines in the spectrum) or increase (anti-Stokes lines), depending on
whether the molecule starts in the ground state or an excited state. Thus, Raman spectroscopy
measures the shift in frequency from that of the excitation laser.
An overwhelming majority of the scattered photons show Rayleigh scattering where
the frequency of the scattered light is same as that of the incdent light. Only a small of a 1000
or 10,000 scattered photons will have a modulated frequency (those will be Raman scattered).
Therefore, the intensity of Raman signal is a millionth of the intensity of incident light (very
less).

28.3.2 Advantages
Raman offers benefits that include minimal sample preparation, the ability to sample
through containers, non-destructive analysis, easy analysis of inorganics, and minimal
interference from water.
Lecture 29 Chemical characterization by spectroscopic
techniques (contd….)

29.1 Electron Spectroscopy

Electron spectroscopy is an analytical technique to study the electronic structure and its
dynamics in atoms and molecules. In general an excitation source such as xrays, electrons or
synchrotron radiation will eject an electron from an innershell orbital of an atom.
Detecting photoelectrons that are ejected by xrays is called xray photoelectron spectroscopy
(XPS) or electron spectroscopy for chemical analysis (ESCA). Detecting electrons that are
ejected from higher orbitals to conserve energy during electron transitions is called Auger
electron spectroscopy (AES).

29.1.2 Auger Electron Spectroscopy (AES)

Auger Electron Spectroscopy (AES) is an analytical technique that uses a primary electron
beam to probe the surface of a solid material. Secondary electrons that are emitted as a result
of the Auger process are analyzed and their kinetic energy is determined. The identity and
quantity of the elements are determined from the kinetic energy and intensity of the Auger
peaks. The nature of the Auger surface analysis process is such that Auger electrons can only
escape from the outer 550 Å of a solid surface at their characteristic energy. This effect
makes AES an extremely surface sensitive technique. A finely focused electron beam can be
scanned to create secondary electron and Auger images, or the beam can be positioned to
perform microanalysis of specific sample features. Applications include materials
characterization, failure analysis, thin film analysis, and particle identification.
 Fig. Auger spectrum for cadmium

29.1.2.1 The Auger Process

a. The basic Auger process starts with removal of an inner shell atomic electron to form
a vacancy. Several processes are capable of producing the vacancy, but bombardment
with an electron beam is the most common.
b. The inner shell vacancy is filled by a second atomic electron from a higher shell.
Energy must be simultaneously released.
c. A third electron, the Auger electron, escapes carrying the excess energy in a
radiationless process.
The process of an excited ion decaying into a doubly charged ion by ejection of an
electron is called the Auger process. Auger process is a three electron process and leaves
atom doubly-ionized.
29.2.2 X-Ray Photoelectron Spectroscopy (XPS)
X-ray photoelectron spectroscopy (XPS) is a surface sensitive quantitative spectroscopic
technique that measures the elemental composition at the parts per thousand range, empirical
formula, chemical state and electronic state of the elements that exist within a material. XPS
spectra are obtained by irradiating a material with a beam of Xrays while simultaneously
measuring the kinetic energy and number of electrons that escape from the top 0 to 10 nm of
the material being analyzed.
X-ray photoelectron spectroscopy works by irradiating a sample material with
monoenergetic soft x-rays causing electrons to be ejected.
• Identification of the elements in the sample can be made directly from the kinetic energies
of these ejected photoelectrons.
• The relative concentrations of elements can be determined from the photoelectron
intensities.
• An important advantage of XPS is its ability to obtain information on chemical states from
the variations in binding energies, or chemical shifts, of the photoelectron lines.
 A typical XPS spectrum is a plot of the number of electrons detected (sometimes per
unit time) versus the binding energy of the electrons detected. Each element produces a
characteristic set of XPS peaks at characteristic binding energy values that directly identify
each element that exists in or on the surface of the material being analyzed. These
characteristic spectral peaks correspond to the electron configuration of the electrons within
the atoms, e.g., 1s, 2s, 2p, 3s, etc. The number of detected electrons in each of the
characteristic peaks is directly related to the amount of element within the XPS sampling
volume.

Fig. XPS spectra

29.3 Ionic Spectroscopy
Ion-scattering spectroscopy has been used extensively to analyze the composition and
structure of solid surfaces.
Various techniques under this methodology are:
a. Rutherford Backscattering Spectrometry (RBS)
b. Secondary ion mass spectrometry (SIMS)
In a typical ISS experiment, a surface is bombarded by noble-gas ions (He+; Ne+; Ar+; Kr+;
Xe+) having a primary energy in the range of 1-20 keV.

The kinetic energy of scattered ions is measured; peaks are observed corresponding to
elastic scattering of ions from atoms at the surface of the sample. Each element at the sample
surface produces a peak at a different measured kinetic energy, caused by the momentum
transfer between the incident ion and atom. The scattered ion and the scattering atom are
normally of different masses, but the total momentum of the atom and ion is conserved.
Therefore, as the initially "stationary" atom recoils, some kinetic energy is lost from the
scattered ion, and the quantity of lost energy depends on the relative masses of the atom and
ion.
An ion scattering spectrum typically contains one peak for each element in the
sample, with their separation in energy relating to the relative atomic masses of those
elements. In some cases, different isotopes of the same element can be resolved. Strong
scattering signals are limited to the topmost layer of atoms, so ISS is extremely surface
sensitive.
 Fig. Ion scattering spectra

29.3.1Rutherford Backscattering Spectrometry (RBS)

 RBS is a thin film characterization technique and relies on the use of very high-energy
beams (MeV) of low mass ions.
 Such ions can penetrate hundreds of nanometers deep into samples and lose their
energies through electronic excitation and ionization of target atoms.
 Sometimes, such fast-moving light ions penetrate the atomic electron cloud shield and
undergo close impact collisions with the nuclei of the much heavier target atoms.
 This results in elastic scattering from the Coulomb repulsion between ion and nucleus,
known as Rutherford Backscattering.
 Information on nature of elements present, their concentration and depth distribution
can be determined by measuring the number and energy of backscattered incident
ions.
29.3.2 Secondary Ion Mass Spectrometry (SIMS)
 SIMS is capable of detecting an extremely low concentration in a solid.
 A source of ions bombards the surface and sputters neutral atoms (for the most part)
along with positive and negative ions from the outermost surface layer.
 Once in the gas phase, the ions are mass analyzed in order to identify the species
present as well as determine their abundance.

29.4 Summary
 AES, XPS and SIMS are true surface analytical techniques, since the detected
electrons and ions are emitted from surface layers less than ~1.5 nm deep.
 AES, XPS and SIMS are broadly applicable to detecting almost all the elements in the
Periodic Table, with few exceptions, whereas EDS can only detect elements with Z>
 11 and RBS is restricted to only selected combinations of elements whose spectra do
not overlap.
 Only RBS is quantitatively precise to within an atomic percent without the use of
composition standards. EDS is the second better choice for quantitative analysis of
chemical compositions. AES, XPS and SIMS all require composition standards for
quantitative analysis and have composition error of several atomic percent.
 XPS, and to a much lesser extent AES, are capable of readily providing information
on the nature of chemical bonding and valence states.