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CHEM F111 : General Chemistry

Lecture 10

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Summary (Lecture 9)
Helium Atom:
-Orbital Approximation
Building up Principle

-Aufbau principle
-Pauli principle

-Hunds rule
-Shielding & Penetration of orbitals

Electronic configuration of atoms & ions

TERM SYMBOLS
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TERM SYMBOLS
For a multi-electron atoms, the spectrum or transitions
between different levels could only be explained if we define a
new system of Term/Energy levels/states that takes into account
the interaction between electrons (in terms of considering the
coupling between orbital and spin angular momentum of
electrons).

In this new system, the energy level of an atom is called a

term, and the notation used to specify the term is a TERM
SYMBOL.
This scheme to arrive at term symbols is called Russell
Saunders coupling.
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Total orbital & spin angular momentum

Total orbital angular momentum could be represented as

L = l1 + l2, l1 + l2 1, l1 + l2 2,.., l1 l2
Clebsch-Gordan Series
Total spin angular momentum could represented as

S = s1 + s2, s1 + s2 1, s1 + s2 2,.., s1 s2
Russell-Saunders coupling

J = L+S, L+S 1, ., |L-S|

Total angular momentum quantum number,
J for multi-electron system.
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Information from Term Symbol

Electronic states of an atom corresponding to its electronic
configuration
Term
Information about S and
multiplicity

Information about L,
Total orbital angular
momentum quantum
number

2S+1

L
Code for conversion
to letter:

Term Symbol
Energy Level

Information about J, Total

angular momentum (spin and
orbital) quantum number

L = 0(S), 1(P), 2(D),

3(F), 4(G), 5(H), 6(I),
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State for a s1 & p1 System System

Configuration: 1s1

Configuration: 1s22s2 2p1

l1 = 0 = L
s1 = 1/2 = S
j = J = 0+1/2, , |0-1/2|
J = 1/2

2S+1

l1 = 1 = L
s1 = 1/2 = S
J = 1+1/2, ., |1-1/2|
J = 3/2, 1/2

S
J

3/2

1/2

1/2

For a given value of J, total number of degenerate states = 2J+1,

distinguished by the quantum no. MJ. J to +J (in integral steps)
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Two p electrons (in different shells 2p13p1)

Excited state configuration of C is [He]2s22p13p1

l1 =1, l2=1
L = l1 + l2, l1 + l2 1, l1 + l2 2,.., l1 l2.
L = (1+1=2), (1+1-1=1),1-1=0.
L = 2(D), 1 (P), 0 (S) DIFFERENT POSSIBLE RELATIVE

ORIENTATIONS OF THE TWO ORBITAL

ANGULAR MOMENTA

S = s1 + s2, s1 + s2 1, s1 + s2 2,.., s1 s2.

s1 = & s2 =

Multiplicity: 2S + 1

S = 1,0

S = 0 (Singlet); S = 1 (Triplet)
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Two p electrons (in different shells 2p13p1)

L = 2(D), 1 (P), 0 (S)

2S+1

S = 1,0

Triplet terms: 3D, 3P, 3S

Singlet terms: 1D, 1P, 1S

J
J = L+S, L+S 1, ., |L-S|

For each term J needs to calculated separately:

A term with different J values represent different level.

For a given term, number

of states (2L + 1)(2S + 1)

For a given conf., number

of states, b!/(b-a)!a!
b: total possible positions:
a : total no of electrons
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Two p electrons (in different shells 2p13p1)

3D

term: L = 2 and S = 1,
So J = 3,2,1. Levels are 3D3
3D
2
3D
1
P term, L = 1 and S = 1,
So, J = 2,1,0. Levels are : 3P2
3P
1
3P
0
3S, : L = 0 and S = 1,
J = 1.
Level is 3S1
1D term: Level is : 1D
2
1P term: Level is: 1P
1
1S term: Level is: 1S
0

7 Degenerate states

15 Deg. states

5 Degenerate states

(2L + 1)(2S + 1)
(2x2+1)(2x1+1)=15

3 Degenerate states

5 Degenerate states

9 Deg. states

3 Degenerate states

(2L + 1)(2S + 1)
(2x1+1)(2x1+1)=9

1 Degenerate states
3 Degenerate states
5 Degenerate states

3 Deg. States

(2x0+1)(2x1+1)=3

3 Degenerate states

5 Deg. States
3 Deg. States

1 Degenerate states

1 Deg. States

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Two p electrons (in different shells 2p13p1)

For a given term, number
of states (2L + 1)(2S + 1)

For a given conf., number

of states, b!/(b-a)!a!
b: total possible positions:
a : total no of electron

3D

term, 15
3P term: 9
3S term: 3
1D term: 5
1P term: 3
1S term: 1
Total no. of states: 36
3D, 3P, 3S, 1D, 1P, 1S

For a 2p13p1
number of states =
6!/(6-1!)1! x 6!/(6-1!)1!

number of states = 36

:All levels exist for this configuration

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Determining the ground state term:

Hunds rule
I The term with the greatest multiplicity lies lowest in energy.
The ground state therefore possesses the most unpaired spins
because this gives the minimum electrostatic repulsion.
So one of the terms 3D, 3P, 3S arising from [He]2s22p13p1
configuration lies lowest.
II The term with the greatest orbital angular momentum lies lowest
in energy.
So 3D term mentioned above will lie lowest of all the terms.
IIIa The level with lowest J lies lowest in energy if the subshell is
less than half filled.
IIIb The level with highest J lies lowest in energy if the subshell is
more than half filled.
Rule III is not applicable for excited configurations.
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G. STATE term symbol determination

Without determining all the levels/states, one can directly
determine the ground state term symbol for any configuration.

Ground State Term should correspond to a term with the

greatest multiplicity (lowest energy) or a state with most
unpaired spins.
For each configuration: We could determine the Ground
State Term by first choosing the max. S (considering ms)
and determine the corresponding max. L possible (by
considering the ml for the orbitals).
ml
ml
+2 +1 0 -1 -2
+1
0
-1
ms
ms
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G. STATE term symbol Determination

Both electrons are
2p1 3p1 Configuration:
For max. S; s1 = & s2 = in parallel spin

2 (D) = Max. L possible

2p1

ML = (1 +1)
3p1

ml
+1

Max. S = 1
=2S+1 = 3

ml
+1

-1

-1

ms

ms

Ground State Term: 3D

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G. STATE term symbol Determination

Both electrons are
2p2 Configuration:
For max. S; s1 = & s2 = in parallel spin

Max. S = 1
=2S+1 = 3

ML= (1 +0)
1 (P) = Max. L possible
ml
2p2
+1
0
-1
ms
Ground State Term: 3P
L = 1 and S = 1,
3P 3P 3P
2,
1,
0
So J = 2,1,0
G.S term of p4 Configuration will be same as p2 confi.,
assuming the filling of holes instead of electrons
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G. STATE term symbol Determination

d3 /d7Configuration:
For max. S s1 =
s2 =
s3 =

three electrons should be Max. S = 3/2

in parallel spin

=2S+1 = 4

3 (F) = Max. L possible

ML= 2 + 1 + 0

ml
+2 +1 0 -1 +2
ms
4F
9/2
4F
7/2
4F
5/2
4F
3/2

Ground State Term: 4F

For a 4F term, J can be calculated

L = 3 and S = 3/2,
So J = 9/2,7/2,5/2,3/2.
Ground State Energy Level (d7 conf.)
Ground State Energy Level (d3 conf.)
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