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# Lecture 20: Complex Atomic Spectra The material in this lecture covers the following in Atkins.

The Spectra of Complex Atoms 13.6 Quantum defects and ionization limits 13.7 Singlet and Triplet States 13. 8 Spin-orbit coupling (a) The total angular momentum (b) Fine structure

Lecture on-line Complex Atomic Spectra (PDF Format) Complex Atomic Spectra (PowerPoint) Handout for this lecture

## Orbitals and orbital energies

Electron configurations
We characterize a many - electron atom by its electron configuration

He : 1s

closed shell

closed shell

2s 1s

2s 1s

2s 1s

2s 1s

2s 1s

## Singlet triplet separation

For both spins up we can have the two possible product functions
r r r r 1s(r1 )(1 )2s(r2 )( 2 ) and 1s(r2 )( 2 )2s(r1 )(1 )
s With the symmetric combination : 1 (1, 2) = r r r r 1s(r1 )(1 )2s(r2 )( 2 ) + 1s(r2 )( 2 )2s(r1 )(1 )

2s 1s

## Singlet triplet separation

a We also have the anti - symmetric combination : 1 (1, 2) = r r r r 1s(r1 )(1 )2s(r2 )( 2 ) - 1s(r2 )( 2 )2s(r1 )(1 )

2s

## Singlet triplet separation

1s For both spins down we can have the two possible product functions

## r r r r 1s(r1 )(1 )2s(r2 )( 2 ) and 1s(r2 )( 2 )2s(r1 )(1 )

s With the symmetric combination : 1 (1, 2) = r r r r 1s(r1 )(1 )2s(r2 )( 2 ) + 1s(r2 )( 2 )2s(r1 )(1 )

2s 1s

## Singlet triplet separation

a We also have the anti - symmetric combination : 1 (1, 2) = r r r r 1s(r1 )(1 )2s(r2 )( 2 ) - 1s(r2 )( 2 )2s(r1 )(1 )

2s 1s

## Singlet triplet separation

For opposite spins we have the two possible product functions r r r r 1s(r1 )(1 )2s(r2 )( 2 ) and 1s(r2 )( 2 )2s(r1 )(1 )

2s 1s
Alternatively, for opposite spins we have the two possible product functions r r r r 1s(r1 )(1 )2s(r2 )( 2 ) and 1s(r2 )( 2 )2s(r1 )(1 ) or 1s(1)(1)2s( 2)( 2) and 1s( 2)( 2)2s(1)(1)

2s 1s
1s 2s

## Singlet triplet separation

2s
2s 1s

1s

We find for the configuration 1s12s1 the following anti - symmetric wave functions

## (1) (2)[1s(1)2s(2) 1s(2)2s(1)]

(1)(2)[1s(1)2s(2) 1s(2)2s(1)]

## (1) (2)[1s(1)2s(2) 1s(2)2s(1)]

MS = 1

ST = 1

S z = h S2 = h 2 S T ( S T + 1) = 2h 2

(1)(2)[1s(1)2s(2) 1s(2)2s(1)]
MS = 1 ST = 1

S z = h S2 = h 2 S T ( S T + 1) = 2h 2

## [ (1)(2) + (1) (2)][1s(1)2s(2) 1s(2)2s(1)]

MS = 0 ST = 1

S z = 0 S2 = h 2 S T ( S T + 1) = 2h 2

MS = 0

ST = 0

Sz = 0 S2 = 0

2s 1s
1s 2s

## Singlet triplet separation

2s
2s 1s

1s

We find for the configuration 1s12s1 the following anti - symmetric wave functions

## (1) (2)[1s(1)2s(2) 1s(2)2s(1)]

S T = 1 ; SM = 1, 0, 1

(1)(2)[1s(1)2s(2) 1s(2)2s(1)]
[ (1)(2) + (1) (2)] [1s(1)2s(2) 1s(2)2s(1)]

## [ (1)(2) (1) (2)] [1s(1)2s(2) + 1s(2)2s(1)]

S T = 0 ; SM = 0 Singlet

## [ (1)(2) + (1) (2)] [1s(1)2s(2) 1s(2)2s(1)]

What is the value of the triplet wavefunction if the two electrons are found at the same position : 1 = ro an 2 = ro

## (1) (2)[1s(r0 )2s(r0 ) 1s(r0 )2s(r0 )] = 0 (1)(2)[1s(ro )2s(ro ) 1s(ro )2s(ro )] = 0

[ (1)(2) + (1) (2)] 1s(ro )2s(ro ) 1s(ro )2s(ro )] = 0
Thus the probability of finding two electrons at the same position for tlet state is zero. This will reduce the electron - electron repulsion

S T = 0 ; SM = 0

Singlet

## [ (1)(2) (1) (2)] [1s(1)2s(2) + 1s(2)2s(1)]

What is the value of the triplet wavefunction if the two electrons are founf at the same position : 1 = ro an 2 = ro

## [ (1)(2) (1) (2)] 1s(ro )2s(ro ) + 1s(ro )2s(ro )] 0

Thus the probability of finding two electrons at the same position for tlet state isnon - zero. This will increase the electron - electron repulsion

sin glet triplet

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

1s 3s

1s12s1

Part of the Grotrian diagram for a helium atom. Note that there are no transitions between the singlet and triplet levels. Transition wavelengths are given in nanometres.

## One can construct different spin - states with different ST values.

Given that everything else is the same (to be explained) the spin - state with the highest ST value has the lowest electron - electron repulsion, and the lowest energy

Why ?

## spin - orbit - coupling

Angular momentum gives rise to a magnetic moment (). For an electron, the magnetic moment is antiparallel to the orbital angular momentum, but proportional to it. L = -(e/2me)L For spin angular momentum, there is a factor 2, which increases the magnetic moment to twice its expected value

S = -(e/me)S

## spin - orbit - coupling

Spin-orbit coupling is a magnetic interaction between spin and orbital magnetic moments.

## cA E L S = < LS > h Here A is referred to as the spin - orbit constant

When the angular momenta are parallel, as in (a), the magnetic moments are aligned unfavourably; when they are opposed, as in (b), the interaction is favourable. This magnetic coupling is the cause of the splitting of a configuration into levels.

## spin - orbit - coupling

We have seen that the spin - orbit interaction energy is given by : cA E= < LS > h

## spin - orbit - coupling

An electron has a spin angular moment with S2 = h 2 (s + 1)s with s = 1/2 S z = hsM where sM = 1 / 2 or 1/2

s l j

An electron has an orbital angular moment with L2 = h 2 (l + 1)l L z = hLM where LM = l, -l + 1, .., l An electron has a total l angular moment with J2 = h 2 ( j + 1)j : j = l + 1/2 and l - 1/2 Jz = hJM where JM = j, j + 1, .., j

## spin - orbit - coupling

We have that the total angular Taking the expectation s momentum vector j is the sum value we get r r v of the orbital angular vector l < l s >= and the spin angular momentum 1 r [< j2 > < s2 > < l2 > ] vector s 2 s r j = l+s r v < l s >= Thus 1 2 r r r r r r h [( j + 1)j s(s + 1) (l + 1)l] j j = ( l + s)( l + s) 2 thus Thus r v j2 = l2 + s2 + 2 l s cA E= < LS > or h r v 1 2 2 1 l s = [ j l s2 ] hcA[( j + 1)j s(s + 1) (l + 1)l] 2 2

## spin - orbit - coupling

Angular momenta opposite The coupling of the spin and orbital angular momenta of a d electron (l = 2) gives two possible values of j depending on the relative orientations of the spin and orbital angular momenta of the electron.

## Angular momenta opposite

cA The levels of a 2P term El,s, j, = < LS > h arising from spin-orbit coupling. 1 Note that the low-j level lies hcA[( j + 1)j s(s + 1) (l + 1)l] below the high-j level. 2

## spin - orbit - coupling

3p1 Fine structure of sodium Fine structure of sodium Fine structure of sodium

3s1

## What you should recall from this lecture

For the electron configuration a1 b1 you should be able to construct the triplet wave functions (1,2)S,m
s

(1, 2)11 = (1) (2)[a(1)b(2) a(2)b(1)] , (1, 2)1,0 [ (1)(2) + (1) (2)] [a(1)b(2) a(2)b(1)] (1, 2)1,1 = (1)(2)[a(1)b(2) a(2)b(1)]

as well as the singlet wave function (1, 2)0,0 = [ (1)(2) (1) (2)] [a(1)b(2) + a(2)b(1)]
For each function be able to evaluate < S2 > and < S z > and explain why the triplets have a lower energy than the singlet

What you should recall from this lecture Realize the qualitative relation between angular momentum and spin magnetic moment

Be able to obtain the j quantum number for the total angular from an electron with the orbit angular momentum quantum number l Be able to calculate the spin orbit splitting for an electron with the orbit angular momentum quantum number l
Understand the qualitative features of Figure 13.27