Quantum Chemistry:

Atomic Structure
Chapter 13

Description of the arrangement of

electrons in atoms
Basis for understanding the
structures and properties of
elements and their compounds
 HYDROGENIC ATOMS
One-electron atom or ion of general atomic
number Z Hydrogenic atom

Hydrogenic atom- H, He+, Li2+, C5+, U91+ etc.

For Hydrogen and Hydrogenic atoms,

Schrdinger equation can be solved exactly

These concepts are used to describe structures

of many-electron atoms and molecules
 Spectrum of Atomic Hydrogen

(n1 =2) (n1 =1)

(n1 =3)
Pfund: (n1 =5)
(n1 =4)

Discrete lines: Energy in H-atom is quantized

Rydberg 1 1 n1= 1, 2,.
formula: RH 2 2 n2= n1+1, n1+2,.
n1 n2 RH=Rydberg constant = 109 677cm-1
 Solution of Hydrogenic atom problem
Two-particles,
three-dimensional system
Ze 2
Potential energy(V) =
40 r
Schrdinger equation:
 Solution of Hydrogenic atom problem
Schrdinger eq. for this problem is better solved
by spherical polar coordinate system

x r sin cos
y r sin sin
z r cos
r 2 x2 y 2 z 2

Schrdinger equation needs to be solved with

proper boundary conditions.
 Solution of Hydrogenic atom problem
The solution for allowed energy levels:
hcRZ 2
En 2
;
n
e 4
mem N
hcR ; me mN
32 0
2 2 2

N = 1,2,3 n is principal quantum number

is the reduced mass
En values are all negative, indicating that
Electron in an atom has lower energy than when
it is free
n=1, E1=-hcRz2
negative sign means
ground state lies hcRz2 below
the energy of the infinitely
separated electron and nucleus
n=2, E2=-1/4 hcRz2
hcR hcR
E 2 2 in a transition
n1 n2
This energy is carried away by a photon of energy
h c which gives R 1 1
n2 n 2
2
1
Energy needed to remove an electron completely
From an atom is ionization energy I=hcRH
 The wavefunctions (atomic orbitals) can be
written as the product of two functions:
R(r)-Radial function & Y(,) angular function

n ,l ,m (l r , , ) Y l , m l ( , ) R n , l ( r )
n, l and ml are called quantum numbers,
arises due to restrictions (boundary conditions)

R(r) depends only on n

and l, while Y(,) depend
only on l and ml
 Quantum Numbers

Principal Quantum number (n) n=1,2,3

Quantization of energy
Orbital angular momentum Quantum number (l)
Quantization of angular momentum magnitude
L l (l 1)
l = 0,1, 2,.., n-1 (n values)
Magnetic Quantum number (ml)
Quantization of angular momentum direction
Lz ml ; m l l , l 1 , l 2 ,............, l
(2l 1) values
 S orbitals
n 1,l 0 , m l 0
The solution of Schrdinger equation gives
1/ 2 r
1 4 r / a0 1
1s 3 e e a0

4
1/ 2
a0
1

a
0
3 2

4 0 2
Bohr radius a 0
mee 2

1s orbital is spherically
symmetrical
 1/ 2
1 4
1s 3 e r / a0
4
1/ 2
a0

This wavefunction decays exponentially towards

zero from 1 1 maximum value at the nucleus
a 0
3 2
H-atom Wavefunction: n ,l ,m l
( r , , ) Y l ,m l ( , ) R n ,l (r )
The probability of finding the electron in the region of space
where its coordinates lie in the ranges r to r + dr, to + d,
and to + d is
2
| | d
Now, What is the probability of finding the
electron in a thin spherical shell centered at
the origin, of inner radius r and outer radius r
+ dr ?

surface
area, 4r2,
thickness, dr

The probability :
 Radial distribution function P(r)
Probability of finding the electron between two spherical shells
of thickness r and r+r is 4 r 2 2 r P ( r ) r

For orbitals (not spherically

symmetrical):
p (r ) r R (r )
2 2

Probability that
an electron will
be found
anywhere in a
shell of radius r
and thickness r
regardless of
angle
 Other s orbitals
2s orbital (n=2, l=0, ml=0) is
also spherical

Wavefunction has nonzero

value at nucleus

It passes through zero

(radial node) before
commencing its experimental
decay towards zero at large
distances

2s orbital has one, 3s orbital

has two, 4s orbital has three
radial nodes
 p orbitals
Y ( , ) R(r) On the nodal plane zero
probability density for electron
1/ 2
3
1/ 2
1 1 r r /2a 0 Zero probability of finding
co s 3 e
4 2 6 a0 a0 electron at the nucleus
1/ 2
1
5
r co s e r / 2 a 0
3 2 a 0

2pz orbital
d orbitals
 Electron spin
Spin of an electron is an intrinsic angular momentum

A purely Quantum mechanical phenomenon

-no classical counterpart
Described by spin quantum number s(1/2)

Analogue of orbital angular momentum

Spin can be clockwise or counterclockwise
Described by spin magnetic quantum number
ms (+1/2 or -1/2)

ms=+1/2 electron ms=-1/2 electron

Two allowed spin states of electron

The magnitude of the spin angular momentum is (31/2/2)

Directions of spin are opposite

 Selection rules for transitions
A photon with its one unit of angular momentum
is generated in a transition
Angular momentum of the electron must change
by one unit to compensate for the angular
momentum carried away by photon
As in linear momentum, angular momentum
must be conserved

l 1 m l 0,1
d(l=2) s(l=0) Not allowed
s(l=0) s(l=0) Not allowed
 Transition dipole moment

s f id
0Transition forbidden

0Transition allowed
Grotrian Diagram
l 1 m l 0,1
 Many electron atoms

All electrons interact with one another

Schrdinger equation is very complicated
Orbital approximation
(Exact wavefunction) ( 1 ) ( 2 ) . . . . .
Pauli Principle

Not more than 2 electrons can occupy one orbital

Spins must be paired when 2 electrons occupy
one orbital
Paired spins
- net spin angular momentum is zero

Li Lowest energy configuration

[He]2s1 or [He]2p1 ?

2s, 2p orbitals are nondegenerate unlike

hydrogenic atoms
An electron in a many-electron atom
experiences repulsion from all other electrons
This is modelled as
point negative
charge on the
nucleus with
magnitude equal to
charge of
electrons within a
sphere of radius r

Ze is changed to Zeffe
Shielded nuclear charge
 Penetration and shielding
Effective nuclear charge experienced by s and p
electrons are different
S electron:
Greater penetration
than p electron
Experiences less
shielding
Experiences larger
Zeff
More close to nucleus
than p electron
 Consequence of penetration and shielding

The order of energies of orbitals in same shell

s<p<d<f

Note:
Individual orbitals of a given subshell are degenerate
They all have same radial character
They all experience same effective nuclear charge

Ground state configuration of Li

1s22s1 or [He] 2s1
 Building up principle

The order of the occupation of orbitals

1s2s2p3s3p4s3d4p5s4d5p6s5d4f6p.

Each orbital can accommodate up to 2 electrons

Electrons occupy different orbitals of a subshell

Before doubly occupying any one

An atom adopts a configuration with the greatest

number of unpaired electrons, in ground state
Hunds rule
 The occupation of d orbitals

Sc(21): [Ar] 3d3 ??

or [Ar] 3d2 4s1

Sc: [Ar] 3d1 4s2

The most probable distance of a 3d electron

from the nucleus is less than that for a 4s
electron.
Periodic trends in atomic properties
Periodic trends in atomic properties
Atomic radii of main-group elements, r/pm
Li Be B C N O F
157 112 88 77 74 66 64
Na Mg Al Si P S Cl
191 160 143 118 110 104 99
K Ca Ga Ge As Se Br
235 197 153 122 121 117 114
Rb Sr In Sn Sb Te I
250 215 167 158 141 137 133
Cs Ba Tl Pb Bi Po
272 224 171 175 182 167
Periodic trends in atomic radii
Periodic trends in first ionization energies