M.

Sc II Semester Chemistry

Term Symbols & Spitting of Terms - Transition Metal

Complexes

Upma Shrivastava
Asstt. Prof.
Govt. V.Y.T.PG.Auto.College
Durg
Chhattisgarh
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 Atomic Term Symbols

Atomic term symbols may be defined as the symbolic representations of various

electronic states having different resultant angular momentums resulting from spin-spin,
orbital-orbital or spin-orbital interactions and the transitions between two different atomic
states may also be represented using their term symbols, to which certain rules apply.
The general form of any atomic term symbol that is used to represent any
electronic state resulting from inter-electronic repulsion is:

2S+1
LJ
Where,
2S+1 = spin multiplicity
S = resultant spin angular momentum quantum number
L = resultant orbital angular momentum quantum number
J = resultant total angular momentum quantum number

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Just like in the case of atomic orbitals, where l represents the individual orbital
angular momentums; L represents the resultants orbital angular momentum of an
electronic state and gives the base designation of any atomic term symbol.

L --- 0 1 2 3 4 5 6 7
STATE --- S P D F G H I K
The letter ‘J’ is omitted since this is used for another quantum number

The calculation of resultant spin and orbital angular momentum involves the
concepts of space quantization and vector interactions. A somewhat simplified
approach for the calculation of resultant orbital angular momentum quantum
number (L), resultant spin angular momentum quantum number S and resultant
total angular momentum quantum number (J) can be given by understanding the
spin-spin, orbital-orbital and spin orbital couplings schemes

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 Rules for determining Term Symbol according to L-S Coupling Scheme

1. l – l coupling:- orbital angular momentum of individual electron is added

vectorially which gives total orbital angular momentum ‘L’ . The possible
values of L are -
L=(l1+l2), (l1+l2-1) , (l1+l2-2) .. .. .. .. .. .. ..|l2-l1|
Here Modulus sign shows that the value of ‘L’ is always positive

2. s- s coupling:- spin angular momentum of individual electron is added

vectorially which gives total spin angular momentum ‘S’
S=(s1+s2), (s1+s2-1), (s1+s2-2) .. .. .. .. .. .. | s2-s1|

3. L-S coupling:- Total orbital angular momentum ‘L’ and total spin angular
momentum ‘S’ are coupled to get total angular quantum number ‘J’
J=(L+S), (L+S-1), (L+S-2) .. .. .. .. .. .. |L-S|

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 Determination of ground state term symbol

To obtain the order of lowest energy level to highest energy level “Hund’s Rule” is
followed -

1. The terms are placed in order depending on their multiplicities i.e. ‘S’ values.
The most stable states has the largest ‘S’ value and stability decreases as
‘S’ decreases. The ground state therefore has the most unpaired spins.

2. For a given value of ‘S’ the state with highest ‘L’ is the most stable.

3. For given values of ‘S’ & ‘L’ , the smallest ‘J’ value is the most stable if the
subshell is less than half filled, and largest ‘J’ value is most stable if the
subshell is more than half filled

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 Hole formulation principle
When a subshell is more than half filled it is simpler and more convenient to
work out the terms by considering the “holes” - that is the vacancies in the
various orbitals, rather than considering the large number of electrons
actually present. The terms derived in this way for the ground state of
oxygen which has a p4 configuration and two holes are the same as for
Carbon with a configuration p2 , that is 1S, 1D, 3P However oxygen has a
more than half filled orbital, when applying Hund’s rule the energy of triplet
‘P’ states for oxygen atom are 3P2 < 3P1 < 3P0 , making 3P2 as ground state. In
a similar way considering “Holes”, atoms with p n and p6-n arrangements and
also dn and d10-n give rise to identical terms.
So, with the help of hole formulation principle we derived terms
only for d , d2, d3, d4 and these terms are also applicable for d 9, d8, d7 and d6
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respectively.
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Derivation of the Term Symbols for unpaired electrons in same subshell

Term symbols for electronic configurations with unpaired electrons in the same subshell can be derived
using "pigeon hole" diagrams. The principal steps for such operations are:

1. Create vertical columns for all allowed orientation or effect of individual orbital angular momentum
in the reference direction. For example, +1, 0 and -1 are the allowed orientations of the orbital
angular momentum corresponding to l = 1 value.

2. Fill up the electrons in these columns by exhausting all the possibilities of parallel, paired and
opposite orientations.

3. Sum-up all the lz values of every column to find out the resultant ‘Lz’ values.

4. Quantum mechanically allowed series set-up should be carried out for different parallel, paired
and opposite orientation, which in turn can be used to provide the resultant orbital angular
momentum quantum number ‘L’ for particular resultant spin quantum number ‘S’.

5. Combine the values of ‘L’ and ‘S’ to find out the term symbols for allowed electronic states.

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For example Term Symbols for d2 and d8 configuration:-

For Parallel Arrangements,

lz
-2 ↑ ↑ ↑ ↑
-1 ↑ ↑ ↑ ↑
0 ↑ ↑ ↑ ↑
+1 ↑ ↑ ↑ ↑
+2 ↑ ↑ ↑ ↑
Lz +3 +2 +1 0 +1 0 -1 -1 -2 -3
Out of ten values of Lz, two quantum-mechanically allowed series can be setup. One with L z = +3, +2,
+1, 0, -1, -2, -3, giving resultant orbital angular momentum quantum number L = 3. The second series
with Lz = +1, 0, -1, giving resultant orbital angular momentum quantum number L = 1. There are two
unpaired electrons, therefore S = 1.
From L = 3 and 1, the states are F and P, respectively. From S = 1, the multiplicity is 3. Thus, the overall
term symbols are 3F and 3P.

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For Paired & Opposite arrangements,
lz
-2 ↑↓ ↓ ↓ ↓ ↓
-1 ↑↓ ↓ ↓ ↓ ↑
0 ↑↓ ↓ ↓ ↑ ↑
+1 ↑↓ ↓ ↑ ↑ ↑
+2 ↑↓ ↑ ↑ ↑ ↑
Lz +4 +2 0 -2 -4 +3 +2 +1 0 +1 0 -1 -1 -2 -3
Out of fifteen values of Lz, three quantum-mechanically allowed series can be setup. First with L z = +4,
+3, +2, +1, 0, -1, -2, -3, -4, giving resultant orbital angular momentum quantum number L = 4.

Second series with Lz = +2, +1, 0, -1, -2; giving resultant orbital angular momentum quantum number
L=2. The third series with Lz = 0 giving resultant orbital angular momentum quantum number L = 0.
There are zero unpaired electrons, therefore S = 0.

From L = 4, 2 and 0 the states are G, D and S, respectively. From S = 0, the multiplicity is 1. Thus, the
overall term symbols are 1G, 1D and 1S.
Hence, for d2 and d8 configurations Term symbols are 1S, 3P. 1D, 3F and 1G.
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Similarly we can calculate Term Symbols for other dn configurations

Configuration Terms
d1, d9 2
D
d2 , d8 3
F , 3P , 1G , 1D , 1S
d3 , d7 4
F , 4P , 2H , 2G , 2F , 2D , 2P
d4 , d6 5
D , 3H , 3G , 3F , 3D , 3P , 1I , 1G , 1F , 1D , 1S
d5 6
S , 4G , 4F , 4D , 4P , 2I , 2H , 2G , 2F, 2D , 2P , 2S

The effect of an octahedral field on S, P, D, and F Terms

‘S’ Term – As ‘s’ orbital is completely symmetrical and also an octahedral field. Then ‘S’ term is orbitally
non degenerate. Since the ligand field potential is concerned only with the orbital part of a wave function,
It cannot split on ‘S’ term . ‘S’ term transforms as A1g in octahedral field.

‘P’ Term – The P term (L=1) has a three fold degeneracy. In an octahedral crystal field all the three ‘p’
orbitals are equally perturved but no splitting occurs, and ‘P’ term transforms as ‘T1g’ in octahedral field

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‘F’ Term – The set of ‘f’ orbital is split by an octahedral field into three levels, two triply degenerate ‘t 2g’
and ‘t1g’ and a single degenerate ‘a2g’ level. Similarly ‘F’ term splits into three level designated as T 1g , T2g
and A2g

‘G’ ‘H’ & ‘I’ Terms – Although ‘G’ , ‘H’ and ‘I’ terms do not occur as ground state terms of ‘d n’ electron
configuration. The result for the splitting of these terms are required in connection with spectra where
excited states are involved.

Transformation of S , P , D , F , G , H & I States

Term Components in an octahedral field
S A1g
P T1g
D Eg + T2g
F A2g + T2g + T1g
G A1g + Eg + T1g + T2g
H Eg + T2g + T1g + T1g
I A1g + A2g + Eg + T1g + T2g + T2g

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 Splitting of D & F terms

The splitting pattern of any term is not dependent on its multiplicity. Some important rule of
splitting is :-
1. When n<5 the splitting of dn+5 is the same as for dn
2. The splitting for d5-n and d10-n are identical
3. Splitting Pattern of d10-n are reverse of that for dn

Eg

+6Dq

-4Dq
T2g

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 A2g
+12Dq

T2g

F +2Dq

-6Dq

T1g

To explain the electronic spectra of complexes generally 3 types of energy level diagrams are
used which are based on this splitting pattern:-
1. Orgel Diagram
2. Tanabe-Sugano Diagram
3. Correlation Diagram

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 Crystal Field Component of ground state and important excited states in octahedral field

dn Free ion ground state Crystal field substates Free ion excited state Ground state term

d1 2
D 2
T2g + 2Eg 2
T2g
d2 3
F 3
T1g + 3T2g + 3A2g 3
P 3
T1g
d3 4
F 4
T1g + 4T2g + 4A2g 4
P 4
A2g
d4 5
D 5
T2g + 5Eg 5
Eg
d5 6
S 6
A1g 6
A1g
d6 5
D 5
T2g + 5Eg 5
T2g
d7 4
F 4
T1g + 4T2g + 4A2g 4
P 4
T1g
d8 3
F 3
T1g + 3T2g + 3A2g 3
P 3
A2g
d9 2
D 2
T2g + 2Eg 2
Eg

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 Energies of crystal field terms in weak octahedral field

dn Energy Examples
d1 2
T2g (-4Dq), 2Eg(+6 Dq) Sc2+ , Ti3+
d2 3
T1g(F) (-6Dq), 3T2g (+2Dq), 3A2g (+12Dq), 3T1g(P) (+15B) Ti 2+ , V3+ , Mo4+
d3 4A2g (-12Dq), 4T2g (-2Dq), 4T1g (F) (+6Dq), 4T1g (P) (+15B) V2+ , Cr3+ , Re4+
d4 5
Eg (-6Dq), 5T2g (+4Dq) Cr2+ , Mn3+ , Ru4+
d5 6
A1g (0) Mn2+ , Fe3+
d6 5
T2g (-4Dq), 5Eg (+6Dq) Fe2+ , Co3+ , Pt4+
d7 4
T1g(F) (-6Dq), 4T2g (+2Dq), 4A2g (+12Dq), 4T1g(P) (+15B) Co2+ , Rh2+
d8 3A2g (-12Dq), 3T2g (-2Dq), 3T1g (F) (+6Dq), 3T1g (P) (+15B) Ni2+ , Pt2+ , Au3+
d9 2
Eg (-6Dq), 2T2g (+4Dq) Cu2+
Here ‘B’ is Racah parameter which is used to evaluate energy difference between states of
the same multiplicity.

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Thank you

Upma Shrivastava
Asstt. Prof.
Govt. V.Y.T.PG.Auto.College
Durg
Chhattisgarh

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