Lecture-11 - 14-11-22

GENERAL CHEMISTRY (CHEM F111)
Lecture 11:14-11-22
Many-electron atoms
•The Schrödinger equation (Ĥ ψ = E ψ) cannot be
solved exactly for atoms with two or more
electrons.
•However, refined approximations allow one to
compute wavefunctions and energies quite
accurately.
•The orbital approximation simplifies the
above equation by assuming that each
electron is associated with a separate one-
electron wavefunction or spin orbital.
Many-electron atoms
Hartree proposed that the
wavefunction could be expressed
simply as a product of spin orbitals,
one for each electron:
ψ(1,2,…) = ψ1(1)ψ2(2)…..
ψ(1,2,…) = ψ1(1)ψ2(2)…..
Each orbital may be thought of as being hydrogen-
like with an effective nuclear charge.
The orbital approximation allows us to
express the electronic structure of an atom in
terms of its:
configuration
the list of occupied orbitals
Add electrons in succession to orbitals of bare

nucleus
He
For example, if one disregards the inter-electronic
repulsion, the ground state wavefunction of He may
be written as
ψ(1,2) = (8/a03)1/2 e-2r1/a0 (8/a03)1/2 e-2r2/a0
corresponding to the configuration
1s2
with the 1s orbital being somewhat more compact
than in H (Nuclear charge being 2).
Li
Three electrons
First two electrons occupy as: 1s2
with the 1s orbital being more compact than in
He (Z=3 for Li)
Next electron? 1s3? NO!!!
A fundamental principle of Nature
•No two identical fermions (½ integer
spin) may occupy the same quantum
state simultaneously.
•Three types of particles from which
ordinary matter is made—electrons,
protons, and neutrons—are all
subject to it.
•Wolfgang Pauli: Pauli exclusion principle
•Impossibility to squeeze identical fermions into
each other - "rigidness" of ordinary matter
Pauli exclusion principle
No more than two electrons may occupy a given
orbital, and if two electrons do occupy one orbital,
then their spins must be paired.
Nobel prize
citation of
Wolfgang
Pauli
The Pauli exclusion principle
No more then two electrons can occupy any given orbital,
and if two electrons do occupy one orbital their spins must
be paired.
 Electrons with paired spins, have zero net spin

angular momentum.
Pauli exclusion principle
The two electrons with paired spins ( have
zero net spin angular momentum.
This principle forms the basis of the electronic
structure of atoms, chemical periodicity, and
molecular structure.
K SHELL COMPLETE! CLOSED SHELL;[He]
The third electron in Li must enter the n = 2 shell,
Three electrons occupy as: 1s2 2s? or 1s2 2p?
Equivalently written as: [He] 2s? or [He] 2p?
Last electron in 2s or 2p??
Are the s and p orbitals degenerate?
• Degenerate in Hydrogenic systems

• Not in many electron systems
• 2s and 2p orbitals are non-degenerate
• p electrons are lower in energy than d,….
• s electrons are lower in energy than p,…

Shielding and Penetration
The effective nuclear charge experienced by
an electron will be determined by its
probability density distribution, and this in
turn by its wavefunction.
In a many electron atom, each electron is
shielded from the nucleus by the others, and
to a first approximation, each electron may
be thought of as experiencing an effective
nuclear charge.
‘s’ electron penetrates more than a ‘p’
electron of the same shell
‘s’ electron experiences a greater effective
nuclear charge than a ‘p’ electron of the same
shell .
The ‘p’ electron experience greater effective
nuclear charge than that for a ‘d’ electron in
the same shell.
In general therefore, in the same shell of a
many-electron atom, the order of energies of
the orbitals is
s < p < d < f.
The ground electronic configuration of Li is
therefore
1s22s1, or [He]2s1.
2s1 is a valence electron
Spectra of complex atoms (Term symbol)
Russell-Saunders Term Symbol
A term symbol is a shorthand notation for indicating

the values of
the orbital, spin and total angular momentum
of an electronic state.
Energy level of an atom : ‘Term’
Notations used to specify the ‘Term’ :
Term Symbols
Useful way to denote electronic states
Atomic States
• Is a specification of the electronic configuration
a complete description of the electronic
structure of an atom?
• Do all states corresponding to a given electronic
configuration have the same energy? NO
• What other properties may be used to describe atomic

states along with the energy?
• What are the other conserved quantities?
Angular Momentum – Orbital, Spin, and Total

Atomic States – Orbital Angular Momentum
• Is the force on each electron in a many electron atom
central?
NO. Consequence?
• Orbital angular momentum of individual

electrons are not conserved, are not ‘good
quantum numbers’
• Total orbital angular momentum is conserved,
is a ‘good quantum number’
• Would like to be able to add angular momenta
Orbital Angular Momentum is quantized
Spin Angular Momentum is quantized
Information from Term Symbol
Information about S
and multiplicity Information about L,
Total orbital angular
2S+1 momentum quantum
number
L
J
Information about J, Total

angular momentum (spin and
orbital)
L – Total (vector sum) orbital angular
momentum number, in spectroscopic
notation
L 0 1 2 3 4
S P D F G
S -represents the vector sum of the spin
angular momentum of the electronic
state
Total Spin Quantum Number
J represents the total angular
momentum of the electronic state
the term symbol would be constructed as
2S+1L
J
Coupling depends on Relative orientations
of orbital and spin angular momenta
Two angular momenta add Two angular momenta oppose
S
Total S
angular
momentum L
L
J=L+S J=L S J=L-S
Vector Addition
Total Orbital angular Momentum L
• Consider two electron with l1 and l2
Term
Vector addition of contributing valence electrons Orbital Value of

l
s 0
p 1
d 2
f 3
g 4
Total Spin angular Momentum S
Spin State
multiplicity
S=0 1 Singlet
. 2 Doublet
s=1/2
s=1/2
s=1/2
3 Triplet
4 Quartet
5 Quintet
6 Sextet
7 Septet
Spin Multiplicity:
8 Octet
Term Symbol
2S+1L
J
value of Spectro-
L scopic code
0 S Example : H(1): 1s1
1 P •L= l = 0 ; i.e. S term
2 D
•S= s = ½ ; 2S + 1 = 2
3 F
4 G •J = j = ½ Term symbol : 2S½
• Total Orbital angular momentum Quantum number L
• L = l1 + l2, l1 + l2  1, l1 + l2  2,.., l1  l2. Clebsch

Gordan series
Total spin Angular momentum Quantum number S
S = s1 + s2, s1 + s2  1, s1 + s2  2,.., s1s2.
Total Angular momentum (Spin & orbital) Quantum number J
J = L+S, L+S – 1, …………., |L-S| 2S+1
2s13s1 L
L=0 implies the term S
J
•l1 = 0 ; l2=0
•s1 = s2= ½ S=1,0 Multiplicity = 3, 1 ;Terms 3S,1S
J=j=1 J= 0 ; Term Symbols : 3S1,1S0

L = l1 + l2, l1 + l2  1, l1 + l2  2,.., l1  l2
S = s1 + s2, s1 + s2  1, s1 + s2  2,.., s1s2.
J = L+S, L+S – 1, …………., |L-S|
2s12p1
L=1 implies the term P
•l1 = 0 ; l2=1
•s1 = s2= ½ S=1,0 2S+1 (Multiplicity) = 3, 1 ;Terms 3 P,1P
L=1, S=1
2S+1
J = 2,1,0 Term Symbols : 3P2, 3P1,3P0 L
L=1, S=0 J
J = 1 Term Symbols : 1P1
The term symbols for 2s12p1 are 3P , 3P ,3P , 1P
2 1 0 1
Part III: Total angular momentum
j - gives relative orientation of spin and orbital

angular momentum of single electron
Total angular momentum quantum number J does
same thing for multi-electron system
J = L+S, L+S – 1, …………., |L-S|

A Clebsch Gordan series
Russel Saunders coupling
As left Term Symbols
superscript As Letters
P,D,….
Multiplicity
of term
Total orbital angular
momentum quantum As right
number, L subscript
Total angular
momentum
quantum number, J
Summary Examples
H (1s1)
ground state term symbol is 2S
1/2
He (1s12s1) An Excited State Configuration
Terms: 1S0 , 3S1
{ There is neither a 3S nor a 3S Term }

0 -1

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GENERAL CHEMISTRY (CHEM F111)

Add electrons in succession to orbitals of bare

 Electrons with paired spins, have zero net spin

• Degenerate in Hydrogenic systems

• p electrons are lower in energy than d,….

• s electrons are lower in energy than p,…

A term symbol is a shorthand notation for indicating

• What other properties may be used to describe atomic

Angular Momentum – Orbital, Spin, and Total

• Orbital angular momentum of individual

Information about J, Total

Vector addition of contributing valence electrons Orbital Value of

• L = l1 + l2, l1 + l2  1, l1 + l2  2,.., l1  l2. Clebsch

J=j=1 J= 0 ; Term Symbols : 3S1,1S0

j - gives relative orientation of spin and orbital

J = L+S, L+S – 1, …………., |L-S|

Terms: 1S0 , 3S1

{ There is neither a 3S nor a 3S Term }

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