Atomic Energy Levels

Spectra of many-electron atoms

• Topics
– L-S (= Russell-Saunders) coupling framework
– terms for non-equivalent electrons
– terms for equivalent electrons
– Hund’s rules for L-S coupling: predicting the ground state
configuration
– j-j coupling

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Many-electron atoms

General considerations
– typically atoms have more than one active electron
– exact solutions to Schrödinger equation formally not possible,
but approximate treatments give essentially correct picture
– L-S coupling (= Russell-Saunders coupling) provides
framework for discussing such atoms in wide variety of
circumstances
– valid unless individual electron spin-orbit coupling dominates
(⇒ j-j coupling)
L-S coupling in many-electron atoms

• L-S coupling issues

– Effects which produced corrections to energy levels:
1. Spin correlation: electron-electron interaction as for helium atom
2. Orbital angular momentum coupling
3. Spin-orbit coupling
– size of effects varies from atom to atom, cannot be trivially predicted
– for low Z atoms (and low n): effects order 1 > 2 »3

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L-S coupling framework
for many-electron atoms
• Spin angular momenta of the electrons couple:
– Total spin angular momentum S = Σ si (vector sum)
– Related total spin angular momentum quantum number S
• Orbital angular momenta of electrons couple:
– Total orbital angular momentum L = Σ li (vector sum)
– Related total orbital angular momentum quantum number L
• Resultant total spin and orbital angular momenta S and L couple to
produce total angular momentum vector J = L + S
• Valid quantum numbers are now:
[s1, s2 ( … sN)], l1, l2 (…lN), L, S, J but not ml1, ms1 … as coupling of l vectors
and s vectors destroys their space quantisation but now have analogous
new projection quantum number for J called mJ .
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Terms for non-equivalent electrons
in many-electron atoms
• Non-equivalent electrons: those which belong to different (n,l) sub-
shells (e.g. orthohelium 1s2s)
• Any (s, l) combination allowed without violating Pauli Exclusion
Principle

• Terms can be worked out using relationships for L, S and J applying

rule for vector addition:
– for two active electrons with spin quantum numbers s1 and s2,
orbital angular momentum numbers l1 and l2:
• S = |s1-s2| … (s1+s2) integer steps l2
• L = |l1-l2| … (l1+l2) integer steps
L
• J = |L-S| … (L+S) integer steps
l1

– equivalent formulae for > 2 electrons (but not considered here)

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For Terms for non-equivalent electrons S=0 L=1 1P

le
examp in many-electron atoms S=0 L=2 1D

S=0 L=3 1F

S=1 L=1 3P

• Examples for non-equivalent electrons:
S=1 L=2 3D

– npnd, i.e., p & d optically active electrons: S=1 L=3 3F

– L = |l1-l2| … (l1+l2) but l1=1, l2=2 ⇒ L = 1, 2, 3
– S = |s1-s2| … (s1+s2) ⇒ S = 0, 1 (s1=s2=½) S=0 L=1 J=1 1P

1
S=0 L=2 J=2 1D2

– produces 6 terms: 1P, 1D, 1F, 3P, 3D, 3F 1
S=0 L=3 J=3 F3

• taking J into account in each case S=1 L=1 J=0,1,2 3P0, 3P1, 3P2

S=1 L=2 J=1,2,3 3D , 3D , 3D

– J = |L-S| … (L+S) 1 2 3
S=1 L=3 J=2,3,4 3F , 3F , 3F

– e.g., for 3F, L=3, S=1 ⇒ J = 2, 3, 4 2 3 4

thus full levels are 3F2, 3F3, 3F4

– in total there are 12 levels for the 6 terms 1P, 1D, 1F, 3P, 3D, 3F
• for each J there are 2J+1 degenerate mJ values
– e.g., npnd configuration: 60 microstates (see next slide)
– same number as expected in decoupled representation, i.e., if angular momentum
coupling and spin correlation were ignored
• e.g., npnd in decoupled representation:
(2l1+1) x (2s1+1) x (2l2+1) x (2s2+1) = 3 x 2 x 5 x 2 = 60 ‘microstates’
• same number of microstates as computed from mJ values

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For
le
examp

Σ = 60
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Terms for equivalent electrons
in many-electron atoms
• Equivalent electrons: those which belong to same (n,l) sub-shells
• Allowed combinations must of course be consistent with Pauli
Exclusion Principle (all quantum numbers cannot be same)
• Simple application of L-S coupling rules used for non-equivalent
electrons produces some terms that are forbidden
– working out valid terms has to be done the hard way

• E.g. simple application for 2p2:

• l1 = l2 = 1 ⇒ L = 0, 1, 2 & S = 0, 1
⇒ apparent terms 1S, 3S, 1P, 3P, 1D, 3D
• But this would result in too many states!
1S 3S 1P 3P 1D 3D

1 + 3 + 3 + 9 + 5 + 15 = 36
• Total number of apparently allowed microstates (36) ≠ number
for decoupled electrons (15) - see next table

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Possible quantum numbers for np2 configuration Note, also avoided
configurations that are
number ml ms ml ms mS mL mJ same due to
1
+1 +½ +1 -½ 0
+2 +2 indistinguishability of
2
+1 +½ 0
+½ +1 +1 +2 electrons.
3
+1 +½ 0
-½ 0
+1 +1
4
+1 +½ -1 +½ +1 0
+1
5
+1 +½ -1 -½ 0
0
0

6
+1 -½ 0
-½ -1 +1 0

7
+1 -½ -1 +½ 0
0
0

8
+1 -½ -1 -½ -1 0
-1
9
0
+½ +1 -½ 0
+1 +1
10
0
+½ 0
-½ 0
0
0

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0
+½ -1 +½ +1 -1 0

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0
+½ -1 -½ 0
-1 -1
must be equivalence
13
-1 +½ 0
-½ 0
-1 -1 between degeneracies
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-1 +½ -1 -½ 0
-2 -2 (=number of allowed
microstates) in the L-S
15
-1 -½ 0
-½ -1 -1 -2 coupled and decoupled
representations
decoupled coupled
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Terms for equivalent electrons
in many-electron atoms
• How to decide which terms are allowed and which terms are forbidden?

• Staying with application for 2p2:

– apparent (i.e. possible w.r.t. s, l values) terms were
• 3D, 1D, 3P, 1P, 3S, 1S
• in fact only 1S, 1D & 3P are allowed, others are forbidden by
application of PEP to decoupled representation

Apply rule: for two equivalent

electrons, states with odd values of
L+S are not allowed.
• Easy to see problem with 3D
– 2p2 & 3D means
• s1= ½, s2= ½, S=1 and thus ms1 = ms2 = ½ (ie spins parallel)
• l1=1, l2=1, L = 2 and thus ml1 = ml2 = +1 (to get L = 2 requires l1 and
l2 to be parallel)
• this is not allowed by PEP in decoupled representation (all qn the
same) and is thus not allowed
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Terms for equivalent electrons
in many-electron atoms: full treatment
• Working rule to sort out valid terms:
– must be equivalence between degeneracies (=number of
allowed microstates) in the L-S coupled and decoupled
representations
• In practice (see previous table for example)
– tabulate all the possible (ml, ms) values for each electron, i.e. for
decoupled representation
– compute the possible values of mS, mL, mJ

– compute apparent terms from s and l values in L-S coupling

scheme (i.e., S, L, J values)
– check that terms are valid by looking to see if appropriate mS, mL,
mJ occur in table
• if not, term is not allowed!

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Terms for equivalent electrons
in many-electron atoms
• Further issues for terms of
equivalent electrons
– closed (full) shells have term Possible terms for equivalent electrons
1S since
0
• all electrons must be ns0 1S

paired, ie. S = Σ si = 0 ns1 2S

• L = Σ li = 0 since ns2 1S

orientations of li must be
such as to give Σmli = 0 np0 1S

– valid terms for subshells of q np1 2P

electrons are the same as for
np2 1S, 1D
3P

subshells with N-q electrons
where N is the closed (full) np3 2P, 2D
4S

subshell complement, np4 1S, 1D

3P

• e.g., p2 has same terms as np5 2P

p4 as N=6 for p subshells np6 1S

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Hund’s rules

• Now know which terms are possible, but which correspond to

ground configuration?
• Hund’s rules give the answer:
– rules give lowest energy term and level for many-electron
atoms
– for L-S coupling
– for ground state configuration of atom only

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Hund’s rules

1. state with highest spin multiplicity has lowest energy ⇒ Smax

2. if more than 1 term with highest spin multiplicity then term with
highest L has lowest energy ⇒ Lmax

3. for terms giving more than 1 level:

• lowest J has lowest energy if outermost subshell is less than half

full ⇒ Jmin if q < N/2

• highest J has lowest energy if outermost subshell is more than

half full ⇒ Jmax if q > N/2

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Examples of application of Hund’s rules
For
le
examp
• Carbon atom: 1s22s22p2
– terms: 1S 3P0, 1, 2 1D

– rule 1 selects 3P?
– rule 3 selects 3P0

• Oxygen atom: 1s22s22p4

– same terms: 1S 3P0, 1, 2 1D

– rule 1 selects 3P?
– rule 3 selects 3P2

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Examples of application of Hund’s rules
For
le
examp

Note, this is excited

state. Hund’s rules
usually (but not always)
work in such cases.

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(1983), (1985)

Application of Hund’s rules

Atom Terms Configuration

H (Z=1) 2S
1s1 2S1/2

He (Z=2) 1S
1s2 1S0

Li (Z=3) 2S
1s2 2s1 2S1/2

Be (Z=4) 1S
1s2 2s2 1S0

B (Z=5) 2P
1s2 2s2 2p1 2P1/2

C (Z=6) 1D, 3P, 1S

1s2 2s2 2p2 3P0

N (Z=7) 4S, 2D, 2P

1s2 2s2 2p3 4S3/2

O (Z=8) 1D, 3P, 1S

1s2 2s2 2p4 3P2

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j-j coupling
• For high Z (and high n at lower Z) the spin-orbit coupling effects
for individual electrons become large
• L-S coupling no longer valid, instead j-j coupling:
– j1 = l1 + s1 for electron 1
– j2 = l2 + s2 for electron 2 ….
… and finally J = Σ ji
• Energy levels different, transition rules different, notation different!
• j-j coupling example:
– 6s6p configuration l1= 0 s1 = ½ ⇒ j1 = ½; l2= 1 s2 = ½ ⇒ j2 = 1/2,
3/2
– notation [j1 j2]J ⇒ [1/2 3/2]2, [1/2 3/2]1, [1/2 1/2]1, [1/2 1/2]0
– if j-j coupling transition 6s6p → 6s2: selection rule ΔJ = 0, ±1
(not 0 → 0)
– if L-S coupling: ΔS=0 ΔL=0, ±1 ΔJ=0, ±1 (not 0 → 0)

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