Chem 373 - Lecture 21: Term Symbols-I

Lecture 21: Term Symbols-I The material in this lecture covers the following in Atkins.
The Spectra of Complex Atoms 13. 9 Termsymbols and selection rules (a) The total orbital angular momentum (b) The multiplicity (c) The total angular momentum
Lecture on-line Term Symbols (PowerPoint) Term Symbols (PDF) Handouts for this lecture
The Term Symbol Total orbital angular momentum For a single electron r Since F is a central force moving around a nuclei r r working in the same direction L = r p as r r p r r r L = r p r r r The angular momentum p r r r L = r p is conserved r with time F r r r r dp dL dr = p+r dt dt dt r r 1 dp r = p+r F = 0 me dt
The Term Symbol Consider next two independent (non - interacting) electrons in the same atom where we neglect the electron - electron repulsion L1 r r L2 p2 r r2 r r r1
Total orbital angular momentum

When we allow the elctrons to interact this is no longer the case r electron L1 r repulsion L2 r p2 p1 r r2 r r r1 electron p1 repulsion
However the total angular momentum L T will still be conserved It can be used to label a state
Angular momentum preserved for each electron !!!
The Term Symbol For a configuration
(n 1l 1m 1)n1 (n 2l 2m 2 )n2 ,...,(n ml mm m )nm

We have a number of different states (eigenfunctions to the Schrdinger equations)
They are characterized by different TERM SYMBOLS : Total spin angular quantum number s T with spin - multiplicity 2s T + 1 2s T + 1 L(l T ) Total orbital angular momentum quantum jT number l T Total angular momentum quantum number j T
The Term Symbol
As an example 2s12p2
Total orbital angular momentum quantum number l T lT : 0 1 2 3 4 S P D F G Total spin angular quantum number s T with spin - multiplicity 2s T + 1
Total angular momentum quantum number j T
The Term Symbol

We must now find
Total orbital angular momentum quantum number l T
Total spin - angular momentum number s T
Total angular momentum quantum number j T
The Term Symbol
Total orbital angular momentum
For the orbital - angular momentum
l(i)z
r L(i)
We have seen that we can find common eigenfunctions to L(i)2 and L(i)z with eigenvalues L(i)2 : h 2 l(i)(l(i) + 1) L(i)z : hm(i); m(i) : - l(i), l(i) - 1, l(i) - 2,...., l(i) - 1, l(i)
Total orbital angular momentum The Term Symbol r r Consider next two angular momenta L(i) and L(j) with the l quantum numbers l(i) and l(j)
r L(i) r LT
Z
r L(j)
r Their sum is a new angular momentum LT with the possible lT quantum numbers lT : l(i) + l( j); l(i) + l( j) 1;.....,| l(i) l( j) |
hm T
r LT
For each lT quantum number the allowed mT values are : - lT ; lT 1;....., lT 1, lT
r 2 2 l (LT) = h lT (lT + 1)
The Term Symbol
Total spin angular momentum
For the spin - angular momentum
S(i)z
r S(i)
We have seen that we can find common eigenfunctions to S(i)2 and S(i)z with eigenvalues S(i)2 : h 2S(i)(S(i) + 1) S(i)z : hmS (i); mS (i) : - S(i), S(i) - 1, S(i) - 2,...., S(i) - 1, S(i)
Total spin angular momentum The Term Symbol s v Consider next two angular momenta S(i) and S(j) with the S quantum numbers S(i) and S(j) r S(j) v r Their sum is a new angular momentum ST with the possible ST quantum numbers S(i)
r ST
ST : S(i) + S( j); S(i) + S( j) 1;.....,| S(i) S( j) |
Z
For each ST quantum number the allowed mS T values are : - ST ; ST 1;....., ST 1, ST
mS T
r ST
r 2 = h 2ST (ST + 1) (ST)
The Term Symbol
Total angular momentum v Consider finally a spin angular momenta S(i) with the S quantum numbers S(i) and an orbital angular r momentum L(i) with the l quantum number l
r S(i) r JT r L(i)
v Their sum is a new angular momentum JT with the possible JT quantum numbers JT : S(i) + l(i); S(i) + l(i) 1;.....,| S(i) l(i) |
The Term Symbol

Z
Total angular momentum
mJ T
r JT
r 2 = h 2J T (J T + 1) (JT)
For each JT quantum number the allowed m J T values are : - JT ; JT 1;....., JT 1, JT
The Term Symbol General procedure for adding the orbital and spin angular momenta in many -electron atoms Consider a multi - electron atom with the electron configuration
(n1l 1m1)n1 (n 2l 2m 2 )n2 ........(nml mmm )nm
Shell 1
Shell 2
Shell n
Ex. He : 1s2; He 1s3d; O 1s2 2s2 2p4; Cl : 1s2 2s2 2p6 3 s 2 3 p 5
Shell 1
Shell 2 Shell n 1. Add orbital - angular momenta of electrons pair - wise # 1+# 2 # I # I +# 3 # II
# II+# 4 ..., L T
Note : add electrons in same shell first A closed shell contributes zero to l T
Shell 1
Shell 2
Shell n
Total orbital angular momentum quantum number l T is indicated by letters lT : 0 1 2 3 4 S P D F G
Shell 1
Shell 2 Shell n 1. Add spin - angular momenta of electrons pair - wise # 1+# 2 # I # I +# 3 # II
# II+# 4 ..., s T
Note : add electrons in same shell first A closed shell contributes zero to s T
Shell 1
Shell 2
Shell n
The s T value of a state is indicated by its spin multiplicity
Spin multiplicity : 2sT + 1 = Number of different m ST values
Shell 1
r S r JT
Shell 2
r L
Shell n
r Finally add L T v and S T
T J2 ; h 2 ( j T + 1) j T where : j T = sT + l T, s T + l T - 1, .. | s T - l T |
The Term Symbol
The total Hamiltonian is h2 h2 Z 1 2 2 Z =1 2 + 1 H 2me 2me r1 r2 r12 We have l (1) = 1; s (1) = 2 1 Omitting at the moment We have l (2) = 2; s (2) = 2 electron - electron repulsion h2 h2 Z 2 2 Z There is (2l(1) + 1)(2s(1) + 1) = H = o 1 2 3 x 2 =6 2me 2me r1 r2 2p spin orbitals
Example He : 2p13d1
There is (2l(2) + 1)(2s(2) + 1) = 5 x 2 = 10 Without electron - electron 3d spin orbitals repulsion all 60 states They can be combined in would have the same energy 6x10 = 60 ways E = 2p + 3d The 2p13d1 configuration has 60 different states
The Term Symbol

Example He : 2p13d1
1 We have l (1) = 1; s (1) = 2 1 We have l (2) = 2; s (2) = 2 Thus combining orbital angular momenta l T = 2 + 1 l T = 2 + 1 1 l T = 2 1 ; ; ; 1 3 2
The total Hamiltonian is h2 h2 Z 1 2 2 Z =1 2 + H 2me 2me r1 r2 r12
When electron - electron repulsion is included states with different LT and S T will have different energy
Next combining spin angular momenta 1 1 s = 1 1; sT = + ; T 2 2 2 2 0 1
The Term Symbol

Example He : 2p13d1
1 We have l (1) = 1; s (1) = 2 1 We have l (2) = 2; s (2) = 2 Thus combining orbital angular momenta l T = 2 + 1 l T = 2 + 1 1 ; ; 3 2 l T = 21 ; 1
(L T , S T )
2S T + 1
(3, 1) (3, 0) (2, 1) (2, 0) (1, 1) (1, 0)
L(L T ) (2 S T + 1) (2L T + 1) Number of States 3 F 21 1 F 7 3 D 15 1 D 5 3 P 9 1 P 3 Total 60
Next combining spin angular momenta 1 1 1 1 sT = + ; sT = ; 2 2 2 2 1 0
States with different spin (L T , S T ) 2S T +1L(L T ) (2 S T + 1) multiplicity will differ in energy. The state withthe higher (2L T + 1) Number of spin - multiplicity will be lower in energy. The energy States 3 (3, 1) F 21 willdecrease with increasing 1 (3, 0) F 7 spin - multiplicity 3 (2, 1) D 15 1 (2, 0) D 5 States with different L T 3 (1, 1) P 9 quantum numbers will 1 (1, 0) P 3 have differentenergies. Total 60 The higher the L T quantum number the lower the energy
The Term Symbol
What you must learn from this lecture For a configuration l (n11m1)n1 (n2l2m2 )n2 ,..., (nmlmmm )nm Be able to construct term symbols : be able to evaluate :
1. Total spin angular quantum number s T and spin - multiplicity 2s T + 1 2.Total orbital angular momentum quantum number lT 3.Total angular momentum quantum number jT NB : remember closed shell adds up to S T = 0 and L T = 0
2s T + 1 L(l T ) jT

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Chem 373 - Lecture 21: Term Symbols-I

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Lecture 21: Term Symbols-I The material in this lecture covers the following in Atkins.

Total orbital angular momentum

Angular momentum preserved for each electron !!!

The Term Symbol For a configuration

(n 1l 1m 1)n1 (n 2l 2m 2 )n2 ,...,(n ml mm m )nm

The Term Symbol

Total angular momentum quantum number j T

The Term Symbol

Total orbital angular momentum quantum number l T

Total spin - angular momentum number s T

Total angular momentum quantum number j T

The Term Symbol

Total orbital angular momentum

For the orbital - angular momentum

For each lT quantum number the allowed mT values are : - lT ; lT 1;....., lT 1, lT

The Term Symbol

Total spin angular momentum

For the spin - angular momentum

r 2 = h 2ST (ST + 1) (ST)

The Term Symbol

The Term Symbol

Total angular momentum

Ex. He : 1s2; He 1s3d; O 1s2 2s2 2p4; Cl : 1s2 2s2 2p6 3 s 2 3 p 5

Total orbital angular momentum quantum number l T is indicated by letters lT : 0 1 2 3 4 S P D F G

The s T value of a state is indicated by its spin multiplicity

Spin multiplicity : 2sT + 1 = Number of different m ST values

The Term Symbol

The Term Symbol

The total Hamiltonian is h2 h2 Z 1 2 2 Z =1 2 + H 2me 2me r1 r2 r12

Next combining spin angular momenta 1 1 s = 1 1; sT = + ; T 2 2 2 2 0 1

The Term Symbol

(3, 1) (3, 0) (2, 1) (2, 0) (1, 1) (1, 0)

L(L T ) (2 S T + 1) (2L T + 1) Number of States 3 F 21 1 F 7 3 D 15 1 D 5 3 P 9 1 P 3 Total 60

Next combining spin angular momenta 1 1 1 1 sT = + ; sT = ; 2 2 2 2 1 0

The Term Symbol

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