Chapter 13

ATOMIC STRUCTURE
Description of the arrangement of
electrons in atoms

Basis
for
understanding
structures
and
properties
elements and their compounds

the
of

HYDROGENIC ATOMS
Hydrogenic atom- H, He+, Li2+, C5+, U91+ etc.
One-electron atom or ion of general atomic
number Z Hydrogenic atom
For Hydrogenic atoms and H,
Schrdinger equation can be solved exactly
These concepts are used to describe structures
of many-electron atoms and molecules

Spectrum of Atomic Hydrogen

Discrete lines
electron energy in H-atom
is quantized

Balmer series:
Rydberg :

1
1
RH 2 2
2 n

1
1

RH 2 2
n1 n2

n= 3, 4,.
RH = 109 677cm-1
n1= 1, 2,
n2= n1+1, n1+2,.
RH=Rydberg constant

n1 =1 Lyman, n1 =2 Balmer, n1=3 Paschen,

n1=4 Brackett, n1=5 Pfund

E h

Bohr frequency condition

Solution of Hydrogenic atom problem

solve Schrdinger by using proper boundary
2
conditions
Ze
The potential energy(V)=
40 r
The solution for allowed energy levels

hcRZ
e 4
me m N
En
hcR

2 2
2
2
32 0
n
me m N
n=1,2,3
is the reduced mass
n is principal quantum number
En values are all negative
Electron in an atom has lower energy than when
it is free
2

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
n2
n1
This energy is carried away by a photon of energy
hc which gives R 1 1
n2
1

n2
2

Energy needed to remove an electron completely

From an atom is ionization energy I=hcRH

Atomic orbitals can be written as the product of

two functions
R(r)-Radial function
Y(,) angular function
R depends on n and l independent of ml
Y(,) depend on l and ml

n ,l , m l ( r , , ) Yl , m l ( , ) R n ,l ( r )

Quantum Numbers
Principal Quantum number (n)
Quantization of energy
Orbital angular momentum Quantum number (l)
Quantization of angular momentum magnitude
L l (l 1)
l = 0,1, 2,.., n-1
Magnetic Quantum number (ml)
Quantization of angular momentum direction

Lz ml

m l l , l 1, l 2 ,......... ..., l
( 2 l 1) values

x r sin cos , y r sin sin

z r cos , r 2 x2 y 2 z 2

S orbitals

n 1, l 0 , m l 0

The solution of Schrdinger equation gives

40
a0
me e 2
Bohr radius

1s

1/ 2

1/ 2

4
3
a0

r / a0

1
1
3 2

r
a0

1s orbital is spherically symmetrical

 1s

1/ 2

1/ 2

4
3
a0

e r / 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 , , ) Yl , 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

What is the probability of the electron having its radial

coordinate between r and r + dr with no restriction on the
values of and ?
i.e., 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 ?

The probability is

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

More general form for orbitals (not spherically symmetrical):

Probability that an
electron will be
found anywhere in
a shell of radius r
and thickness r
regardless of angle

p (r ) r R (r )
2

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

Other s orbitals

p orbitals
Y ( , )
1/ 2

3

4

On the nodal plane zero

probability density for electron

R(r)
1/ 2

1 1
cos 3
2 6 a0
1/ 2

5
32

a
0

r cos e r / 2 a0

2pz orbital

r r / 2a 0
e
a0

Zero probability of finding

electron at the nucleus

d orbitals

Electron spin
Spin of an electron is an intrinsic angular momentum
Quantum mechanical phenomenon -no classical
counterpart
Electron spin is described by spin quantum number(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

l 1 m l 0, 1
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
d(l=2)
s(l=0)

s(l=0) Not allowed

s(l=0) Not allowed

Transition dipole moment

s f i d
0 Transition forbidden
0 Transition allowed

Grotrian Diagram

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-zero net spin angular momentum

Li

Lowest energy configuration

[He]2s1 or [He]2p1 ?
Penetration and shielding

2s, 2p orbitals are nondegenerate unlike

hydrogenic atoms
Electron at distance r from nucleus experiences
repulsion

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

Effective nuclear charge experienced by s and p

electrons are different
S electron
Greater penetration through inner shells than p
electron

More likely to be found close to nucleus than p

electron
Experiences less shielding

Experiences larger Zeff

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

Atomic radii of main-group elements, r/pm

Li

Be

157

112

Na

Mg

Al

Si

191

160

143

118

110

104

Ca

Ga

Ge

As

Se

Br

235

197

153

122

121

117

114

Rb

Sr

In

Sn

Sb

Te

250

215

167

158

141

137

133

Cs

Ba

Tl

Pb

Bi

Po

272

224

171

175

182

167

88

C
77

N
74

66

64
Cl
99

Periodic trends in atomic radii

Periodic trends in first ionization energies