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

Spectra of Complex Atoms

Orbitals and orbital energies

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

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

He : 1s

closed shell

Li : 1s2 2s1 F : [He] 2s2 2p5 Cl : [Ne] 3s2 3p5

closed shell

Spectra of Complex Atoms

Singlet triplet separation

Consider the configuration 1s12s1 for the excited state of He

We can have 4 orientations of the spins

2s 1s

2s 1s

2s 1s

2s 1s

Spectra of Complex Atoms

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 )

s 1 (1, 2) is symmetric in the interchange of electron 1 and 2 s s or 1 (1, 2) = 1 ( 2, 1)

Spectra of Complex Atoms

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 )

a 1 (1, 2) is anti - symmetric in the interchange of electron 1 and 2 s s or 1 (1, 2) = 1 ( 2, 1)

Only anti - symmetric wave functions are acceptable

Spectra of Complex Atoms

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 )

s 1 (1, 2) is symmetric in the interchange of electron 1 and 2 s s or 1 (1, 2) = 1 ( 2, 1)

Spectra of Complex Atoms

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 )

a 1 (1, 2) is anti - symmetric in the interchange of electron 1 and 2 s s or 1 (1, 2) = 1 ( 2, 1)

Only anti - symmetric wave functions are acceptable

Spectra of Complex Atoms

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)

Spectra of Complex Atoms

Singlet triplet separation

From these you can form two anti - symmetric combinations

anti symmetric in spin symmetric in [ (1)(2) (2)(1)][1s(1)2s(2) + 1s(2)2s(1)] space

symmetric in spin [ (1)(2) + (2)(1)][1s(1)2s(2) 1s(2)2s(1)] anti - symmetric in space

Spectra of Complex Atoms

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)]

symmetric in spin anti - symmetric in space

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

anti symmetric in [ (1)(2) (1) (2)][1s(1)2s(2) + 1s(2)2s(1)] spin symmetric in space

Spectra of Complex Atoms

Singlet triplet separation

(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

Spectra of Complex Atoms

Singlet triplet separation

[ (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

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

MS = 0

ST = 0

Sz = 0 S2 = 0

Spectra of Complex Atoms

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)]

Triplet : 3 times degenerate in S2

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

S T = 0 ; SM = 0 Singlet

Spectra of Complex Atoms

Singlet triplet separation

S T = 1 ; SM = 1, 0, 1 Triplet (1) (2)[1s(1)2s(2) 1s(2)2s(1)] (1)(2)[1s(1)2s(2) 1s(2)2s(1)]

[ (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

Spectra of Complex Atoms

S T = 0 ; SM = 0

Singlet triplet separation

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

Spectra of Complex Atoms

sin glet triplet

Singlet triplet separation

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.

Spectra of Complex Atoms For a configuration

Singlet triplet separation

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

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 ?

Spectra of Complex Atoms

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

Spectra of Complex Atoms

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.

Spectra of Complex Atoms

spin - orbit - coupling

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

How do we find the expectation value : <LS >

Spectra of Complex Atoms

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

Spectra of Complex Atoms

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

Spectra of Complex Atoms

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 alined

Spectra of Complex Atoms

spin - orbit - coupling

Angular momenta alined

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

Spectra of Complex Atoms

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