ELECTRONIC STRUCTURE OF ATOMS

From Classical Physics to Quantum Theory

CLASSICAL PHYSICS VS. QUANTUM THEORY

CLASSICAL PHYSICS Can explain acceleration, projectiles and freely falling bodies Can be used to predict and explain certain macroscopic properties of molecules such as pressure Viewed energy as continuous and any quantity of which can be released. Cannot explain forces that hold atoms together Principles do not govern phenomena at atomic and molecular level Described molecules as bouncing marbles and balls (COLLAPSING ATOM PARADOX) QUANTUM THEORY Led to scientific proposals of epic proportions New era in Physics started in 1900s by Max Planck Can be understood by the nature of waves Max Planck devised a relationship between energy and frequency.

PROPERTIES OF WAVES
WHAT IS A WAVE? Vibrating disturbance by which energy is transmitted. PROPERTIES OF WAVES
PROPERTY FREQUENCY AMPLITUDE
WAVELENGTH SPEED

DEFINITION No. of peaks passing per second Peak height above midline
Peak to peak distance Distance per time

SYMBOL A

UNITS m/s, cm/s, nm/s Varies with type of wave

m, cm, nm

u/c Cycle/s, Hertz *c for speed of light

ELECTROMAGNETIC RADIATION
In 1865, James Clerk Maxwell proposed that visible light is composed of electromagnetic waves(radiation). This radiation is composed of oscillating electric and magnetic fields, perpendicular to each other and to the direction of the travel.

ELECTROMAGNETIC RADIATION
Speed of electromagnetic waves is equal to 8 the speed of light which is 3 x 10 m/s(vacuum) Electromagnetic radiation is emission and transmission of energy in the form of electromagnetic waves. These types of waves can be emitted or absorbed by atoms. This principle is known as Maxwell theory.

ELECTROMAGNETIC RADIATION

PLANCKS QUANTUM THEORY

Electromagnetic radiation is emitted over wide range of wavelengths when solids are emitted. Planck gave the name quantum to the smallest quantity of energy that can be emitted or absorbed in the form of electromagnetic radiation The energy, E of a single quantum is -34 E = h where h = Plancks constant, 6.63 x 10 J-s Quantum Theory states that energy is transmitted in multiples of h

PHOTOELECTRIC EFFECT
In 1905, Albert Einstein used the concept of Quantum Theory to explain photoelectric effect. Einstein asserted that light consisted of bundles of energy that can carry and transfer energy like particles paving the way to the concept of wave-particle duality.

BOHRS THEORY OF HYDROGEN ATOM

EMISSION PROCESS IN AN EXCITED H ATOM Niels Bohr explained emission spectrum of H atom(earned him Nobel Peace Prize for Physics) Continuous or line spectra of radiation is emitted by excited substance. Bohr postulated that electron is allowed to Moving from one orbit to another occupy only certain orbits of causes atom to absorb or emit a specific energies. photon of energy

Emission process is analogous to a ball moving either up or down a set of stairs.

Notes on the Bohr Model

1. Zero energy is the point at which the proton and electron are infinitely separated; energy must be absorbed to reach this state, so all states below it have negative energy. 2. The ground state is the lowest energy state for the hydrogen atom, where n = 1. Any n value above 1 corresponds to an excited state. 3. When an electron emits energy as a photon of light, it falls from a higher n to a lower n.

DUAL NATURE OF THE ELECTRON

Bohrs model is limited to hydrogen atom and does not explain the wavelike properties of electron. When applied to atoms with two or more electrons, the theory gives only qualitative agreement with experimental data Dual nature of electrons wave and matter Louis de Broglie (1892-1987) who was working on his Ph.D. degree at the time, made a daring hypothesis: If radiant energy could, under appropriate circumstances behave as though it were a stream of particles, then could matter, under appropriate circumstances, exhibit wave-like properties? De Broglie suggested that the electron could be thought of as a wave with a characteristic wavelength.

QUANTUM MECHANICS
Bohrs approach cannot explain the line spectra of hydrogen atom when magnetic field is applied. De Broglies postulate led to the development of Quantum Mechanics. From Quantum Mechanics:
Kinetic energy of an electron is inversely related to the volume of the region to which it is confined. The kinetic energy increase from the shrinking volume of an electron moving toward the nucleus balances the electrostatic attraction to prevent the electron from falling into the nucleus It is impossible to specify the precise position of an electron in an atom at a given instant (HEISENBERG UNCERTAINTY PRINCIPLE)

LINE SPECTRA

 Erwin Schrodinger (1887-1961)

Wrote a differential equation to express the wave properties of an atom
is called the wave function It is possible to find the amplitude of the electron wave at various points in space 2 is proportional to the probability of finding an electron at a particular point in space

Electron Cloud Diagrams

Electron cloud diagrams are maps of electron density
The depth of color is proportional to 2, the probability of finding an electron

Orbitals
The orbital represents the region in space where there is a 90% or higher probability of finding an electron

QUANTUM NUMBERS
QUANTUM NUMBERS: derived from the mathematical solution of Schrodinger equation. Set of four numbers describing an electron in an orbital Approximations allow for solutions of the equation relevant to atoms with two or more electrons The solutions result in orbitals, which have an energy, a shape and an orientation in space

Principal Quantum Number, n

The principal energy level is specified by the first quantum number, n It describes the overall energy of the level n = 1, 2, 3, 4, (integral values)
n = 1 is the first principal level n = 2 is the second principal level, and so on

 Each principal energy level (specified by n) has one or more sublevels

The sublevel is specified by the quantum number is derived from n:
= 0, 1, 2 (n-1) In the nth principal level, there are n sublevels

Angular Momentum (Azimuthal) Quantum Number,

Instead of using numbers, the sublevels are given letter designations

For = 0, 1, 2, 3 we use s (0), p(1), d(2), f(3) Determines the shape of the sublevel orbital

Azimuthal Quantum Number

Magnetic Quantum Number, m

Each sublevel contains one or more orbitals, which differ from one another in the value of the third quantum number, m Just as depends on n, m depends on
m = +1, 0, -1, - There are 2 + 1 orbitals per sublevel

Determines the spatial orientation of the sublevel orbital

Spin Quantum Number, ms

The last quantum number is associated with the electron spin
Two spins are possible, clockwise and counterclockwise There are two values of ms, + and

The Pauli Exclusion Principle

No two electrons in the same atom may have the same set of four quantum numbers
Two electrons may occupy an orbital; these will differ in spin The spins of two electrons in an orbital will be opposite to each other

EXERCISES

1. Consider the following set of quantum numbers( n, l, ml, ms), which would not occur? Explain your answer. a. 3, 2, 0, c. 2, 1, -1 , -1/2 b. 4,3, -2, 0 d. 1, 1, 0, 2. What is the capacity for electrons of a p sublevel? f sublevel? 3. What is the total capacity of electrons of the third principal level? 4. Write the quantum nos. of the ff: a. 5p b. 4d c 4f d 3p5

HOMEWORK
Write the quantum numbers of the following electronic configuration. 1 1. 4s 8 2. 5d 3. 4p 6 4. 5f 10

ATOMIC ORBITALS
s (sharp) : all s sublevels are spherical differing only by size. As n increases the radius of the orbital becomes larger. p(principal): consists of two lobes along an axis d(diffuse): floral in shape. f(fundamental): has a complex shape

ELECTRON CONFIGURATIONS
Describes arrangement of electron in an atom By applying the rules from which quantum numbers derive, it is possible to assign quantum numbers to each electron in an atom
Electron configuration: 1s22s22p5 Coefficient is n Letter is m Superscript is the number of electrons

Electron Configuration from Sublevel Energies

Once the order of filling of sublevels is known, the electron configuration is readily obtained
Experimental evidence provides the relative energies of sublevels Sublevels are ordinarily filled before proceeding to the next energy sublevel

Examples
H, 1s2 He, 1s2 Li, 1s22s1 Be, 1s22s2 B, 1s22s22p1 C 1s22s22p2

The Transition Metals

Consider Ar: 1s22s22p63s23p6
The next electron enters the 4s
K: 1s22s22p63s23p64s1 Ca: 1s22s22p63s23p64s2

With the transition metals, the 3d fills after the 4s

Sc: 1s22s22p63s23p64s23d1

Following the transition metals, the 4p fills

Ga: 1s22s22p63s23p64s23d104p1

Abbreviated Electron Configurations

To save writing, abbreviated electron configurations are written
Start with the preceding noble gas Complete the configuration with the rest of the electrons in the element
S is [Ne]3s23p4 Ni is [Ar]4s23d8

Filling of Sublevels and the Periodic Table

By using the periodic table, it is possible to quickly write an electron configuration for any element
Consider the Group 1 elements
All have the outer configuration s1

Consider the Group 2 elements

All have the outer configuration s2

Atoms of elements in a group have the same distribution of electrons in the outermost principal energy level

Notes on The Periodic Table

1. 2. 3. 4. Elements in Group 1 and 2 fill an s sublevel Elements in Groups 13-18 fill a p sublevel Elements of the transition metals fill a d sublevel The two sets of 14 elements each at the bottom of the periodic table fill f sublevels with a principal quantum number two less than the period number
First row: lanthanides Second row: actinides

Exceptions
Some elements have electron configurations that differ from those expected from the application of the rules we have seen
Cr is actually [Ar]4s13d5 Cu is actually [Ar]4s13d10

These difference arise because

The energy levels of the orbitals are close to each other There is a gain in stability by producing a half-filled or a filled shell where possible

Orbital Diagrams of Atoms

One step beyond the assignment of electrons to orbitals is the depiction of electrons in orbitals
Parentheses indicate orbitals (__) Arrows, up and down, indicate electrons ()
Recall the ms quantum number One electron in an atom has ms = and the other has ms =

Hunds Rule
Maximize unpaired spins where possible

Figure 6.10

Notes
In all filled orbitals, the two electrons have opposed spins Within a given sublevel there are as many halffilled orbitals as possible
This is a direct consequence of Hunds Rule

Hunds rule is based on experiment

Substances with unpaired electrons are paramagnetic Substances with all paired electrons are diamagnetic

Electron Arrangements in Monatomic Ions

In forming an ion, electrons are removed from (cation) or added to (anion) sublevels in the highest principal energy level Main Group Ions and Noble Gas Structures Cations of Group 1 form +1 ions Cations of Group 2 from +2 ions Nitrogen forms a -3 ion Elements in the oxygen family form -2 ions Halogens form -1 ions

Transition Metal Cations

Transition metal cations do not form ions with noble-gas configurations
Cations do form, with charges ranging from +1 to higher numbers The outer s electrons are lost before the d electrons; this is the first-in, first-out rule

Consider Mn
Mn is [Ar]4s23d5 Mn2+ is [Ar]3d5

EXERCISES
1. Write the electron configuration of the following elements using long method and draw their orbital diagrams: a. Ca b. P c. Cr 2. Write the core method electron configuration of the following elements: a. Ge b. Ag c. La 3. Write the ground state electron configuration 23+ for a. S, S b. Al, Al c. Fe, Fe2+

Periodic Trends
The chemical and physical properties of elements are a periodic function of atomic number
Recall that the number of electrons is equal to the atomic number of an element Properties to be considered
Atomic radius ionic radius Ionization energy Electronegativity Electron Affinity

Atomic Radius
The size of an atom is a difficult to define term The radius of an atom can be defined and measured, assuming the atom is a sphere The trend for the radius of the atom is
A decrease in radius across a period An increase in radius down a group

Trends in Atomic Radius

The increase in radius down a group can be explained by the decreases in effective nuclear charge The decrease in radius across a period can be explained by increases in effective nuclear charge

Ionic Radius
Cations are smaller than the atoms from which they form
Fewer electrons mean increased effective nuclear charge on those that remain

Anions are larger than the atoms from which they form
More electrons mean that there is more electron-electron repulsion so the size of the ion increases relative to that of the atom

Ionization Energy
The ionization energy is a measure of difficulty in removing an electron from a gaseous atom M (g) M+ (g) + e Ionization energy increases across a period from left to right Ionization energy decreases down a family from top to bottom

Electronegativity
Electronegativity is the ability of an atom to attract electrons
Linus Pauling
Fluorine is the most electronegative element Cs is the least electronegative element

As electronegativity increases, the formation of an anion becomes more likely

Trends
Electronegativity increases across a period Electronegativity decreases down a family

Table 6.5

Electron Affinity
Energy associated with addition of electron to atom or ion. If the process is exothermic then electron affinity has a negative value. Trend: EA increases across the periodic table EA decreases down a group

EXERCISES
Arrange the following atoms according to the given trend: a. Increasing atomic radius: Al, Na, S, Cl b. Decreasing ionization energy: Sb, P, Bi, As, N c. Increasing electronegativity: Ru, Sr, I, Sn, Rb d. Increasing Ionic Size: Cu , Cu2+ Cu+ , e. Decreasing tendency to gain e-: At, Cl, I, F, Br f. Decreasing tendency to lose e-: Ba, Bi, Po, Cs, Pb