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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

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

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

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

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

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

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

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)]

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

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

2s

2s 1s

1s

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

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)]

S T = 0 ; SM = 0 Singlet

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) + (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

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

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

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.

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 ?

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 is a magnetic interaction between spin and orbital magnetic moments.

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.

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

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

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

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.

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

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

3s1

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

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