Lecture on-line 14 Molecular structure The Born-Oppenheimer approximation

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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 2p1 3d1

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

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

The Term Symbol

Example He : 2p1 3d1
1 r 12

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

1P

1D

1F 1 1 2p 3d

3P

3D

3F

Adding to the Hamiltonian Example He : 2p1 3d1 h2 h2 Z 1 2 2 Z =1 2 + H 1 2me 2me r1 r2 r12 We have l (1) = 1; s (1) = 2 An interaction between the 1 orbital angular momentum We have l (2) = 2; s (2) = r 2 L and the spin - angular T Thus combining orbital r momentum S T in terms angular momenta of the spin - orbit interaction l T = 2 + 1 l T = 2 + 1 1 ; ; r r 3 2 term Hso = aL T S T Gives rise to the Hamiltonian l T = 21 ; H1 = H + aL S 1 With this Hamiltonian states with Next combining spin the sameL T and S T but different angular momenta JT will have different energies 1 1 1 1 1 EL,S,J = hc {J(J + 1) L(L + 1) sT = + ; sT = ; 2 2 2 2 2 S(S + 1)} 1 0

The Term Symbol

The Term Symbol

Example He : 2p1 3d1

1 r 12

Spin-orbit interaction

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 ; ; 1 1 2p 3d 3 2 l T = 21 ; 1
Next combining spin angular momenta 1 1 1 1 sT = + ; sT = ; 2 2 2 2 1 0

1P

1P 1 1D

1D

1F

1F

3P

3D

3F

3P 2 3P 1 3P 0 3D 3 3D 2 3D 1 3 F4 3F 3 3F 2

The Term Symbol

Example He : 2p1 3d1

1 We have l (1) = 1; s (1) = 2
1 We have l (2) = 2; s (2) = 2

Finally combining S T and L T to construct J T

L T = 3 , ST = 1 J T = 3 + 1, 3 + 1- 1, 3 - 1 4 3 2
Term Symbols :
3

Thus combining orbital angular momenta

F4; 3 F3 ; 3 F2

; l T = 2 + 1 l T = 2 + 1 1 l T = 2 1 ; ; 1 3 2
Next combining spin angular momenta 1 1 1 1 sT = + ; sT = ; 2 2 2 2 0 1

L T = 3 , ST = 0 JT = 3+0 3
Term Symbols :
1

F3

The Term Symbol

Example He : 2p1 3d1

1 We have l (1) = 1; s (1) = 2
1 We have l (2) = 2; s (2) = 2

Finally combining S T and L T to construct J T

L T = 2 , ST = 1 J T = 2 + 1, 2 + 1- 1, 2 - 1

Thus combining orbital angular momenta

Term Symbols :
3

D3; 3 D2 ; 3 D1

; l T = 2 + 1 l T = 2 + 1 1 l T = 2 1 ; ; 1 3 2
Next combining spin angular momenta 1 1 1 1 sT = + ; sT = ; 2 2 2 2 0 1

L T = 2 , ST = 0 JT = 2+0
2

Term Symbols :
1

D2

The Term Symbol

Example He : 2p1 3d1

1 We have l (1) = 1; s (1) = 2
1 We have l (2) = 2; s (2) = 2

Finally combining S T and L T to construct J T

L T = 1 , ST = 1 J T = 1+ 1, 1+ 1- 1 , 1- 1

Thus combining orbital angular momenta

Term Symbols :
3

P2; 3 P1 ; 3 P0

; l T = 2 + 1 l T = 2 + 1 1 l T = 2 1 ; ; 1 3 2
Next combining spin angular momenta 1 1 1 1 sT = + ; sT = ; 2 2 2 2 0 1

L T = 1 , ST = 0 J T = 1+ 0 1
Term Symbols :
1

P2

The Term Symbol 1 Spin-orbit

r 12 interactio

(l T , S T , j ) (3,1, 4) (3,1, 3) (3,1, 2) (3, 0, 2) (2,1, 3) (2,1, 2)

3P 2 3P 1 3P 0 3D 3 3D 2 3D 1 3 F4 3F 3 3F 2

2 S T +1 3 3 3 1 3 3 3 1 3 3 3 3

L(l T ) j

2j +1 9 7 5 7 7 5 3 5 5 3 1 3 60

F4 F3 F2 D3 D2 D1 P2 P1 P0 P1 Total

1P 1D

1P 1 1D

F3

1F

1F

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

3P

D2

3D 3F

The Term Symbol 1 Spin-orbit

r 12 interactio

1P 1D

1P 1 1D

For less than half filled sub shells, states (within a TERM of equal L T and S T ) with lowest J T has lowest energy

1F

1F

3P

3D 3F

3P 2 3P 1 3P 0 3D 3 3D 2 3D 1 3 F4 3F 3 3F 2

For more than half filled sub shells, states (within a TERM of equal L T and S T ) with higest J T has lowest energy

The Term Symbol 1 Spin-orbit

r 12 interactio

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

1P 1D

1P 1 1D

1F

1F

3P

3D 3F

3P 2 3P 1 3P 0 3D 3 3D 2 3D 1 3 F4 3F 3 3F 2

All filled shells or subshells give L T = 0 and S T = 0. They can be disregarded

The Term Symbol

In electronic transitions we start with the electron configuration (A) (n1l 1m1)n1 (n 2l 2m 2 )n2 .(nil im j )ni (nkl kmk )ni ........(nml mmm )nm
of TERM symbol
2S T (A) S

of TERM symbol
2S T (B) S

L(LT (B)) J T (B)

For elements 1- 80 Such a transition is only allowed if

L(LT (A)) J T (A)

1. l i l k = l = 1 since absorbed photon has l = 1

2. S T (A) - S T (B) = S = 0 a photon has no spin

we next move an electron from shell (i) to shell (k) to produce the new configuration (B) (n1l 1m1)n1 (n 2l 2m 2 )n2 .(nil im j )ni 1 (nkl kmk )nk +1........(nml mmm )nm

3. L T (A) - L T (B) = L = 0, 1 Note we can still have L = 0 and l (i) - l (k) = 1

The Term Symbol

sin glet triplet

S = (1s)1(ns)1 P = (1s)1(np)1 D = (1s)1(nd)1 F = (1s)1(nf )1

1. l i l k = l = 1 since absorbed photon has l = 1

1s13s1 1s12s1

2. S T (A) - S T (B) = S = 0 a photon has no spin

3. L T (A) - L T (B) = L = 0, 1 Note we can still have L = 0 and l (i) - l (k) = 1

The Term Symbol

For a many - electron atom with the LT quantum number the possible m quantum numbers are m = LT , LT 1, LT 2, ...., - LT

For each ml we have an angular momentum along the z - axis of Lz = hml and a magnetic moment z = Bml

The Term Symbol For each m we have an angular momentum l along the z - axis of Lz = hml and a magnetic moment z = Bml

The magnetic moment can interact with an external magnetic field B along the z - axis to give E = - zB = BmlB

The Term Symbol

The normal Zeeman effect. On the left, when the field is off, a single spectral line is observed. When the field is on, the line splits into three, with different polarizations. The circularly polarized lines are called the (-lines; the plane-polarized lines are called (-lines. Which line is observed depends on the orientation of the observer.

The Term Symbol What you should recall from this lecture
Selection rules for electronic transitions S = 0 , L = 0, 1, l = 1 J = 0, 1; but J = 0 to J = 0 not allowed

You should recall spliting in and external magnetic field B of levels with same L quantum as Eml = B mlB ml = L,L - 1,...., -L - 1, -L