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CHEM F111 General Chemistry Lecture 10

Many electron atoms, aufbau, spin-
orbit interactions
 Review of lecture 09

• Radial functions of hydrogenic atoms

• Emission spectra of hydrogenic atoms
• Spin angular momentum, bosons and fermions
• Pauli principle, antisymmetry in many-electron
wavefunction.
• Orbital approximation, spin-orbitals, antisymmetric
wavefunctions for paired and unpaired electronic
states
• Singlets and Triplets
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Orbital approximation

No two electrons can have same spin-orbital. (Pauli

principle revisited)
If two electrons have same spatial orbital, then their
spins must be different (paired).
The two electrons with paired spins have zero net spin
angular momentum. (S=0, hence, MS=0).
An orbital can accommodate maximum two electrons.
This principle forms the basis of the electronic
structure of atoms, chemical periodicity, and
molecular structure.
The third electron in Li must enter the n = 2 shell, but
the 2s or the 2p?
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Order of occupation
The penetration of an ‘s’ electron is greater as
compared to a ‘p’ electron of the same shell implies
that it experiences a greater effective nuclear charge.
The 's' electron also shields the nucleus more
effectively as compared to the 'p' electron resulting in
more stability. In turn, the effective nuclear charge
experienced by the ‘p’ electron will be greater than that
for a ‘d’ electron in the same shell and the 'p' electron
would shield the nucleus more effectively than a 'd'
electron.
In general therefore, in the same shell of a many-
electron atom, the order of energies of the subshells is
s < p < d < f.
Thus, the ground electronic configuration of Li is
therefore 1s22s1, or [He]2s1.
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Order of occupation

Aufbau principle: (Building up principle)– The subshells

are occupied in the sequence:

1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s, 4f, 5d, 6p,
7s, …

Every orbital has two spin-parts resulting in two spin-

orbitals. Thus, every orbital can accommodate two
electrons. Consequently, a subshell with azimuthal
quantum number, l, can accommodate 4l+2 electrons.

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Ground state electronic
configuration (under orbital approximation)
H: 1s1 F: [He]2s22p5

He: 1s2 Ne: [He]2s22p6

Li: 1s22s1 → [He]2s1 Na: [He]2s22p63s1 → [Ne]3s1

Be: 1s22s2 → [He]2s2 Al: [Ne]3s23p1

B: 1s22s22p1 → [He]2s22p1 Ar: [Ne]3s23p6

C: 1s22s22p2 → [He]2s22p2 Sc: [Ar]3d14s2

N: 1s22s22p3 → [He]2s22p3 Zr: [Kr]4d15s2

O: 1s22s22p4 → [He]2s22p4 Ce: [Xe]4f15d16s2

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Electronic configuration of
atoms
Question: How many states of a Carbon atom
correspond to the electronic configuration: 1s22s22p2 ?
Answer: The 1s and 2s subshells are completely filled.
The two electrons in 2p subshell can be arranged in
6
C2 = 15 possible ways → 15 states.
Question: Are all these states energetically
degenerate?
Answer: No. Not all of them have same energy.
Question: What are the factors affecting the energies
of these states?
Answer: Coupling of the spin and orbital angular
momenta – spin orbit interactions.

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Orbital and spin angular
momenta
Are they independent?
Magnetic moment from spin
Electron has spin angular momentum
Moving charges generate magnetic fields
Magnetic field generated from spin
Magnetic moment from orbital angular momentum
Electron has orbital angular momentum if l>0.
In effect a circulating current
Magnetic field generated from orbital momentum
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Magnetic moments due to
angular momenta
l HIGH ENERGY
Magnetic moments are
parallel (angular
momenta are parallel)
s
l LOW ENERGY
Magnetic moments are
antiparallel (angular
momenta are
antiparallel)
s
Energy depends on relative orientation of spin- and
orbital- angular momenta
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Spin orbit coupling for one
electron
Vector addition: j = l + s
Case: j = l + s Case: j = |l – s|

j s
l  l 
Components of vectors
add like scalars: j
mj = ml + ms
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Spin orbit coupling

Energy of the spin-orbit coupling depends on

E α {j(j+1) – l(l+1) – s(s+1)}
For electron, s= ½;
If orbital angular momentum is zero then; l=0 →
j=s=½
E α {j(j+1)–l(l+1)–s(s+1)} ={½(½+1)–0 –½(½+1)}=0
No spin orbit coupling.
In other cases, spin-orbital coupling will result in
change in the energy → different energy levels obtained

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Spin orbit coupling in many-
electron atoms – heavy atoms
For heavy atoms, the effective nuclear charge is very
large, consequently, the magnetic moments induced in
the electrons as a result of relative motions of nuclei
(corresponding to orbital and spin motions of
electrons) are very large. The orbital magnetic moment
and the spin magnetic moment of each electron
strongly couple to give the total electronic magnetic
moment corresponding to the total angular momentum
of an electron, (quantum number j). The total angular
momentum of the atom (quantum number J) is
obtained by adding the total angular momenta of all
the electrons – j-j coupling.

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Spin orbit coupling in many-
electron atoms – light atoms
For light atoms, the effective nuclear charge is
relatively small. The spin-orbit interactions are very
small and to a very good approximation, one can
calculate the total orbital angular momentum of the
atom (quantum number L; vector sum of the orbital
angular momenta of all electrons) and analogously, the
total spin angular momentum (quantum number S) of
the atom. The total angular momentum of the atom
(quantum number J) can be viewed as the resultant of
the total orbital and total spin contributions – LS
coupling. In this course, we will briefly study only the
LS coupling. Also known as RS coupling after Russell
Saunders

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Terms and levels
The set of electronic states of an atom corresponding
to a given set of total orbital angular momentum and
total spin angular momentum constitute a term.
Using the total angular momentum quantum number
(L) and total spin angular momentum quantum
number, the term is represented by term symbol of
the form:
2S+1
(spectroscopic symbol for L)
Spectroscopic symbols are: S,P,D,F,G,H,I... for
L=0,1,2,3,4,5,6....
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Terms and Levels
Upon considering the spin-orbit interactions, the term
splits into levels characterized by the total angular
momentum quantum number, J. The levels of a term
are represented by subscripting the total angular
momentum quantum number (J) on the right of the
corresponding term symbol:
2S+1
(spectroscopic symbol for L)J.
J=L+S, L+S-1,....., |L-S|

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Terms and levels for one-
electron atoms

For a single electron case, there L=l and S=s, and

consequently, there is only one term. For L=l=0,
there is only one level with J=S=s; whereas, for L>0,
there are two levels.
e.g.
L=l=0 → term: 2S → level: 2S1/2

L=l=1 → term: 2P → levels: 2P3/2 and 2P1/2

L=l=2 → term: 2D → levels: 2D5/2 and 2D3/2 and so on.

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Terms and levels for many-
electron atoms
Example: two electron case -
Electronic configuration 1s2: L=l1+l2=0; S=0 because

the electrons are paired. Hence, the only term is 1S

with the only level, 1S0.

What about the electronic configuration 1s12s1 ?

Since the electrons are unpaired, there are four
possible spin-orientation resulting in a triplet (S=1)
and a singlet (S=0), the terms are 3S and 1S with
levels, 3S1 and 1S0, respectively.
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Terms and levels for many-
electron atoms
Terms and levels for e.c. 1s22s1? – same as for 1s1
(Term: 2S; Level: 2S1/2)

Terms and levels for e.c. 1s22s2or 1s22s22p6? – same

as for 1s2 (Term: 1S; Level: 1S0)

Observation: s-subshells do not contribute to L,

completely subshells do not contribute to L and S.
Terms and levels for e.c. 1s22s12p1?
L = 1, S=1,0 → Terms: 3P, 1P
Levels for 3P: 3P2, 3P1, 3P0; Levels for 1P: 1P1
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Terms and levels for many-
electron atoms

Terms and levels for e.c. 1s22s22p13p1?

L = 2,1,0; For each L; S=1 or 0
Terms:3D,1D, 3P, 1P, 3S, 1S
Levels for 3D: 3D3, 3D2, 3D1; Levels for 1D: 1D2

Levels for 3P: 3P2, 3P1, 3P0; Levels for 1P: 1P1

Levels for 3S: 3S1; Levels for 1S: 1S0

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Terms and levels for many-
electron atoms
Terms and levels for e.c. 1s22s22p2?
This case is slightly complicated. Since both the
electrons are in the same p-subshell, Pauli principle
will restrict the spin orientations – paired electrons
cannot have parallel spins.

First we note that the number of states (possible

electronic arrangements) for the e.c. = 6C2 = 15

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Terms for many-electron atoms

Terms and levels for e.c. 1s22s22p2: (Continued)

We will first collect all possible electronic distributions in
spin-orbitals of 2p subshell based on the (ML,MS) values.

ml=1

ml=0

ml=-1

ML 2 0 -2 1 1 1 1 0 0 0 0 -1 -1 -1 -1
MS 0 0 0 1 0 0 -1 1 0 0 -1 1 0 0 -1
Term D
1
D
1
D
1
P
3
D
1
P
3
P
3
P
3
P
3
S
1
P
3
P
3
D
1 3
P 3
P
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Terms and levels for many-
electron atoms
Terms and levels for e.c. 1s22s22p2: (Continued)
1. Start with the highest value of ML → we have ML=2.

2. Locate the configuration with maximum value of MS

corresponding to this. → MS=0 for ML=0.

3. Since these are maximum values of ML and MS, the

corresponding term must be with L=2, S=0 → 1D.

4. 1D has (2S+1)(2L+1)=5 states corresponding to MS=0

and ML=2,1,0,-1,-2. Mark these states with term, 1D

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Terms and levels for many-
electron atoms
5. Is there still any unmarked configuration with ML=2? No.

6. Among the unmarked configurations, search the one with

next highest value of ML and repeat the procedure till all

configurations are marked. Repeat the procedure till all ML=0

configurations are marked.

Following this procedure, we get the term 3P with 9 states
corresponding to (2S+1)(2L+1) for ML=(1,0,-1);MS=(1,0,-1).

At last we are left with ML=0, MS=0 → L=0, S=0

corresponding to the term, 1S.

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Terms and levels for many-
electron atoms
Levels for e.c. 1s22s22p2:
We have obtained the terms; 1D, 3P and 1S.
Levels are obtained by calculating J=L+S,L+S-1,....|L-S| for
every term. Consequently, we have
D → 1D2
1

P → 3P2, 3P1, 3P0

3

S → 1S0
1

The degeneracy of a given level J is (2J+1).

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Lowest energy terms and levels

The lowest energy terms and levels are obtained by

applying Hund's three rules of maximum multiplicity.
1. The first rule says that the lowest term would be
the one with maximum spin multiplicity.
2. The second rule says that if two or more terms
have the highest spin multiplicity, then among them,
the term with maximum orbital multipicity (quantum
no. L) will lie the lowest.
3. The third rule says about the ordering of levels of
the lowest energy term. If the subshell is less than
half full, the level with smallest value of J lies the
lowest in energy. If the subshell is greater than half
full, the level with highest value of J lies the lowest in
energy.
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Ground term and level
If one wants to obtain the term and level only for
ground (or the lowest) state, then the same can be
obtained very easily without calculating the other
possible terms and levels.
To get the ground (or the lowest energy) term for a
configuration, arrange the electrons in the subshell
with leading to maximum spin multiplicity. Calculate
the maximum value of ML that can be possible for this
configuration which will be same as the L for the
ground term.
The lowest level can be obtained using the Hund's
third rule.
e.g. nitrogen: 1s22s22p3: ML=0 → L=0; S=3/2 → Term
is 4S, level is 4S3/2.
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An imperical rule for terms of a
doubly occupied subshell
If all the subshells (except one) of an atom are either
completely filled or completely vacent and only one subshell
(with azimuthal quantum number l) is doubly occupied, then
the possible values of L are 2l, 2l-1, 2l-2,....,0
Since both the electrons are occupying the same subshell, the
restriction due to Pauli principle results in triplet terms from
odd values of L and singlet terms from the even values of L.
e.g. it can be easily justified that –
An nd2 configuration has the terms: 1G, 3F, 1D, 3P, 1S
An nf2 configuration has the terms: 1I, 3H, 1G, 3F, 1D, 3P, 1S
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