Many Electron Atoms

Helium Spectra and Pauli Exclusion Principle

IDENTICAL PARTICLES
• In quantum mechanics the uncertainty principle does not allow us to
observe constantly the motion of the electrons without changing their
behavior.
• An accurate quantum mechanical treatment of these systems must be
formulated in such a way that the indistinguishability of identical
particles is explicitly taken into account.
• Let us consider two identical and indistinguishable particles, each of
mass m and their respective coordinates x1,y1,z1 and x2,y2,z2. Then
𝜓 𝑇 (𝑥1 , … , 𝑧2 ) = the eigenfunction for the total system
𝑉𝑇 𝑥1 , … , 𝑧2 = the potential energy for the total system
𝐸𝑇 = the total energy for the total system
• We assume that there is no interaction between the two particles, the
particles move independently.
• Then 𝑉𝑇 𝑥1 , … , 𝑧2 = 𝑉 𝑥1 , 𝑦1 , 𝑧1 + 𝑉 𝑥2 , 𝑦2 , 𝑧2
• 𝜓 𝑇 (𝑥1 , … , 𝑧2 ) = 𝜓(𝑥1 , 𝑦1 , 𝑧1 )𝜓(𝑥2 , 𝑦2 , 𝑧2 )
• Each of the eigenfunctions describing one of the particles requires three
quantum numbers to specify the mathematical form of its dependence on its
three space coordinates.
• In addition, each requires one more quantum number to specify the orientation
of the spin of the particle.
• We shall shorten the notation by using a single symbol, such as 𝛼, 𝛽, 𝛾, etc., to
designate a particular set of the four quantum numbers required to specify the
space and spin quantum state of one of the particles.
• The total eigenfunction 𝜓 𝑇 (𝑥1 , … , 𝑧2 ) for the case in which particle 1 is in the
state 𝛼, and particle 2 is in the state 𝛽, is
𝜓 𝑇 𝑥1 , … , 𝑧2 = 𝜓𝛼 1 𝜓𝛽 (2)
and probability density is 𝜓 𝑇∗ 𝜓 𝑇 = 𝜓𝛼∗ 1 𝜓𝛽∗ (2) 𝜓𝛼 1 𝜓𝛽 (2)
• The total eigenfunction 𝜓 𝑇 (𝑥1 , … , 𝑧2 ) for the case in which particle 2 is in the
state 𝛼, and particle 1 is in the state 𝛽, is
𝜓 𝑇 𝑥1 , … , 𝑧2 = 𝜓𝛽 (1)𝜓𝛼 2
and probability density is 𝜓 𝑇∗ 𝜓 𝑇 = 𝜓𝛽∗ 1 𝜓𝛼∗ 2 𝜓𝛽 1 𝜓𝛼 2

Due to indistinguishability, we would expect

𝜓𝛼∗ 1 𝜓𝛽∗ (2) 𝜓𝛼 1 𝜓𝛽 (2) 1⟶2 𝜓𝛽∗ 1 𝜓𝛼∗ 2 𝜓𝛽 (1)𝜓𝛼 2
2⟶1
• But it is apparent that the relabelled probability density function is not equal to
the original probability density function.
• Therefore, we must conclude that these are not acceptable eigenfunctions for
the accurate description of a system containing two identical particles.
Let us consider linear combination of the eigenfunctions
1
𝜓𝑆 = (𝜓𝛼 1 𝜓𝛽 (2) + 𝜓𝛽 (1)𝜓𝛼 2 ) →Symmetric wavefunction
2

1
𝜓𝐴 = (𝜓𝛼 1 𝜓𝛽 (2) − 𝜓𝛽 (1)𝜓𝛼 2 ) →Antisymmetric wavefunction
2

By an exchange of the particle labels

1 1
𝜓𝑆 = (𝜓𝛼 1 𝜓𝛽 (2) + 𝜓𝛽 (1)𝜓𝛼 2 ) 1⟶2 (𝜓𝛼 2 𝜓𝛽 (1) + 𝜓𝛽 (2)𝜓𝛼 1 ) = 𝜓𝑆
2 2
2⟶1

1 1
𝜓𝐴 = (𝜓𝛼 1 𝜓𝛽 (2) − 𝜓𝛽 (1)𝜓𝛼 2 ) 1⟶2 (𝜓𝛼 2 𝜓𝛽 (1) − 𝜓𝛽 (2)𝜓𝛼 1 ) = −𝜓𝐴
2 2
2⟶1

We then have for the probability densities

𝜓𝑆∗ 𝜓𝑆 1⟶2 𝜓𝑆∗ 𝜓𝑆 and 𝜓𝐴∗ 𝜓𝐴 1⟶2 −1 2 𝜓𝐴∗ 𝜓𝐴
2⟶1 2⟶1

Hence, for both the symmetric and antisymmetric total eigenfunctions, the probability
density functions are not changed by an exchange of the particle labels.
THE EXCLUSION PRINCIPLE
• In a multi-electron atom there can never be more than one electron in
the same quantum state.
• Now consider the antisymmetric total eigenfunction, for a case in which
both particles are in the same space and spin quantum state α.
1
𝜓𝐴 = (𝜓𝛼 1 𝜓𝛼 (2) − 𝜓𝛼 (1)𝜓𝛼 2 ) = 0
2
• Hence, if two particles are described by the antisymmetric total
eigenfunction, they cannot both be in a state with the same space and
spin quantum numbers.
• Thus, a system containing several electrons must be described by an
antisymmetric total eigenfunction.
• For a system with N electrons, the antisymmetric total wavefunction is
given by the Slater determinant
 EXCHANGE FORCES AND THE HELIUM ATOM
• Consider a pair of electrons in a system in which we can ignore any explicit
interactions (like the Coulomb interaction) between the two particles. Then
1
𝜓𝐴 = (𝜓𝛼 1 𝜓𝛽 (2) − 𝜓𝛽 (1)𝜓𝛼 2 )
2
• This antisymmetric total eigenfunction depends on both the space variables
and the spin variables of the two electrons.
• Total eigenfunction = (space eigenfunction) x (spin eigenfunction)
• Let
1
𝜓𝑆 = (𝜓𝑎 1 𝜓𝑏 (2) + 𝜓𝑎 (1)𝜓𝑏 2 ) →Symmetric space eigenfunction
2
1
𝜓𝐴 = (𝜓𝑎 1 𝜓𝑏 (2) − 𝜓𝑎 (1)𝜓𝑏 2 ) →Antisymmetric space eigenfunction.
2
• Symbols and b represent a particular set of the three space quantum
numbers.
 1 Exchange Forces
[(+1/2,-1/2) −(-1/2,+1/2)] → Antismmetric spin eigenfunction (Singlet)
2
• There are three possible symmetric spin eigenfunctions
(+1/2,+1/2)
1
[(+1/2,-1/2) +(-1/2,+1/2)] (Triplet State)
2
(-1/2,-1/2)
 Exchange Forces

• If the spins of the two electrons are "parallel" and the spin eigenfunction is
one of the symmetric triplets, the space eigenfunction must be antisymmetric,
in order to have the total eigenfunction antisymmetric.
• Let us consider such a situation for a case in which the space variables of the
two electrons happen to have almost the same values. Then
𝜓𝑎 1 𝜓𝑏 2 ≈ 𝜓𝑏 1 𝜓𝑎 2
In this case the value of the antisymmetric space eigenfunction is
1
𝜓𝐴 = 𝜓𝑎 1 𝜓𝑏 2 − 𝜓𝑎 1 𝜓𝑏 2
2
1
= (𝜓𝑎 1 𝜓𝑏 (2) − 𝜓𝑎 (1)𝜓𝑏 2 ) = 0
2

• The result is that the probability density will be very small when the triplet
state electrons have similar coordinates, i.e., when they are close together.
• Since there is little chance of finding them close together, the triplet state
electrons act as if they repel each other.
 Exchange Forces

• Symmetric space eigenfunctions have inverse properties.

1
𝜓𝑆 = 𝜓𝑎 1 𝜓𝑏 2 + 𝜓𝑎 1 𝜓𝑏 2
2
1
= (𝜓𝑎 1 𝜓𝑏 (2) + 𝜓𝑎 (1)𝜓𝑏 2 ) = 2𝜓𝑎 (1)𝜓𝑏 2
2
Probability density will be 2𝜓𝑎∗ 1 𝜓𝑏∗ (2) 𝜓𝑎 1 𝜓𝑏 (2)
• So there is a particularly large chance of finding the two noninteracting
electrons close together if their space eigenfunction is symmetric.
• Thus, if the spins of the two electrons are "antiparallel" and the spin
eigenfunction is the antisymmetric singlet, the space eigenfunction
must be symmetric.
• The singlet state electrons act as if they attract each other since there
is a large chance of finding them close together.
• The two electrons in He act as if they move under the influence of a
force whose sign depends on the relative orientation of their spins.
• This is called an exchange force. It is a purely quantum mechanical effect
and has no classical analogy.
 Helium Spectra

• For each singlet state there is a corresponding triplet state except for the ground state.
• The triplet states lie a little deeper than the corresponding triplet state.
• The energy difference between the ground and the first excited state is relatively larger.
• The triplet states do not combine with the singlet state as selection rule for transitions
∆𝑆 = 0
Ground state energy of He
• Hamiltonian for He atom

• The Schroedinger Eq

• If the two electrons are considered independent then

Ground State energy of He

The ground state energy of Helium = -79 eV

• Considering electron repulsion:

Perturbed Part

Unperturbed Part
• Correction in ground state energy
Atomic Structure and the Periodic Table

 What would happen if there are more than one electron?

a nucleus with charge +2e attracting two electrons.
the two electrons repelling one another.

 Can not solve problems exactly with the Schrödinger equation because
of the complex potential interactions.

 Can understand experimental results without computing the wave

functions of many-electron atoms by applying the boundary conditions
and selection rules.

13
Atomic Structure
Hydrogen: (n, ℓ, mℓ, ms) = (1, 0, 0, ±½) in ground state.
 In the absence of a magnetic field, the state ms = ½ is degenerate with
the ms = −½ state.

Helium: (1, 0, 0, ½) for the first electron.

(1, 0, 0, −½) for the second electron.
 Electrons have antialigned (ms = +½ and ms = −½) spins as being
paired. Supports Pauli exclusion principle.

 The principle quantum number also has letter codes.

 n = 1 2 3 4...
Electrons for H and He atoms are in
 Letter = K L M N… the K shell.
H: 1s2
He: 1s1 or 1s
 n = shells (eg: K shell, L shell, etc.)
 nℓ = subshells (eg: 1s, 2p, 3d)

14
Atomic Structure
How many electrons may be in each subshell?
Total
For each mℓ: two values of ms 2
For each ℓ: (2ℓ + 1) values of mℓ 2(2ℓ + 1)

Recall: ℓ = 0 1 2 3 4 5 …
letter = s p d f g h …
ℓ = 0, (s state) can have two electrons.
ℓ = 1, (p state) can have six electrons, and so on.

The lower ℓ values have more elliptical orbits than the

higher ℓ values.
Electrons with higher ℓ values are more
shielded from the nuclear charge.
Electrons lie higher in energy than those with
lower ℓ values.
4s fills before 3d. 15
16
17
18
The Periodic Table

19
Angular Momentum Coupling

• We have already learned that in the one-electron system,

the individual angular momenta l and s combine to give a
resultant angular momentum j.
• There is a similar coupling between the angular momenta of
different electrons in the same atom.
• We consider cases in angular momentum coupling: the LS or
Russell-Saunders coupling, and jj coupling.
• Electrons in orbitals with same n and l are said to be
equivalent. For example ground state of He 1s2
• Electrons in orbitals with different n or l are said to be non-
equivalent. For example the first excited state of He 1s2s
LS or Russell-Saunders coupling
• Now, we will find out the terms using the rules for
the coupling of angular momenta are
Total orbital angular momentum (L) of a p and a
d electron (p1d1 configuration)

L= l1 + l2, l1 + l2 – 1,..., |l1 + l2| = 3, 2, 1

P
Multiplicity (2S+1) of two electrons each with
spin angular momentum = 1/2

S = s1 + s2, s1 + s2 – 1,..., |s1 - s2| = 1, 0

Triplet

Singlet
• This is used for most atoms when the magnetic field is weak.

J = L+S, L+S-1,..., |L-S|

• For given L, there are 2S + 1 values of J.

• For L > S, J goes from L − S to L + S.
• For L > S, there are 2S + 1 possible J values.
• The value of 2S + 1 is the multiplicity of the state.
• For L < S, there are fewer than 2S + 1 possible J values.
• Then the value of 2L + 1 is the multiplicity of the state.
25
J = L+S, L+S-1,..., |L-S|
• The notation for a single-electron atom becomes
n2S+1 LJ
• The letters and numbers are called spectroscopic symbols.
• There are singlet states (S = 0) and triplet states (S = 1) for two electrons.

27
Excited State Configurations of He (1s2)

If L = 0 and S = 0 ⟹ 𝐽 = 0 → 1S 0
If L = 0 and S = 1 ⟹ 𝐽 = 1 → 3S 1

If L = 1 and S = 0 ⟹ 𝐽 = 1 → 1P1
If L = 1 and S = 1 ⟹ 𝐽 = 0,1,2 → 3P0,1,2
 If L = 2 and S = 0 ⟹ 𝐽 = 2 → 1D2
If L = 2 and S = 1 ⟹ 𝐽 = 1,2,3 → 3D1,2,3

Excited State Configurations of Carbon (1s22s22p2)

If L = 2 and S = 0 ⟹ 𝐽 = 2 → 1D2
If L = 2 and S = 1 ⟹ 𝐽 = 1,2,3 → 3D1,2,3
If L = 1 and S = 0 ⟹ 𝐽 = 1 → 1P1
If L = 1 and S = 1 ⟹ 𝐽 = 0,1,2 → 3P0,1,2
If L = 0 and S = 0 ⟹ 𝐽 = 0 → 1S 0
If L = 0 and S = 1 ⟹ 𝐽 = 1 → 3S 1
Equivalent electron configurations
Here, the crossed terms will not survive because of the Pauli Exclusion principle.
Now for finding the terms, start with highest ML = 0 and highest MS = 0. This
will arise from L = 0 and S = 0. The degeneracy is 1. So the terms is 1S0 .
np2 configuration

ml 1 0 -1 1 0 -1
ms 1/2 1/2 1/2 -1/2 -1/2 -1/2
a b c d e f

ab ac ad ae af
bc bd be bf
cd ce cf
de df
ef

ab ac ad ae af bc bd be bf cd ce cf de df ef
ML 1 0 2 1 0 -1 1 0 -1 0 -1 -2 1 0 -1
MS 1 1 0 0 0 1 0 0 0 0 0 0 -1 -1 -1
 ab ac ad ae af bc bd be bf cd ce cf de df ef
ML 1 0 2 1 0 -1 1 0 -1 0 -1 -2 1 0 -1
MS 1 1 0 0 0 1 0 0 0 0 0 0 -1 -1 -1

Maximum value of ML = 2, corresponding MS = 0

Ml 2 1 0 -1 -2 1D
Ms 0 0 0 0 0 2

Next higher value of ML = 1, corresponding MS = 1

ML 1 0 -1 1 0 -1 1 0 -1 3P
0,1,2
MS 1 1 1 0 0 0 -1 -1 -1

Remaining value of ML = 0, corresponding MS = 0, i.e., 1S0

 Breit Scheme np2 configuration
ml1 1 0 -1
Set -1: 2 1 0 -1 -2 1D
ML 2 1 0 1 Set -2: 1 0 -1 3P
2

0,1,2
ML 1 0 -1 0 Set 3: 0 1S
0
ML 0 -1 -2 -1
S P D ml2

nd2 configuration
ml1 2 1 0 -1 2
Set -1: 4 3 2 1 0 -1 -2 -3 -4 1G
ML 4 3 2 1 0 2 3F
4
Set -2: 3 2 1 0 -1 -2 -3 2,3,4
ML 3 2 1 0 -1 1 Set -3: 2 1 0 -1 -2 1D
2
ML 2 1 0 -1 -2 0 Set -4: 1 0 -1 3P
0,1,2
Set -5: 0 1S
ML 1 0 -1 -2 -3 -1 0

ML 0 -1 -2 -3 -4 -2
S P D F G ml2
Selection rules
 The allowed transitions for the LS coupling scheme are
 ΔL = ±1 ΔS = 0
 ΔJ = 0, ±1 (J = 0 → J = 0 is forbidden)

 A magnesium atom excited to the 3s3p triplet state has no lower

triplet state to which it can decay.
 It is called metastable, because it lives for such a long time on
the atomic scale.

35
 Hund’s Rules

 State with the largest value of S is most stable and stability

decreases with decreasing S.
 For states with same values of S, the state with the largest
value of L is the most stable.
 If states have same values of L and S then, for a subshell
that is less than half filled, state with smallest J is most
stable; for subshells that are more than half filled, state with
largest value of J is most stable.

36
 Hund’s rules (equivalent electrons, LS)
1. Largest S has the lowest energy
2. Largest L with the same S has the lowest energy
3. For atoms with less-than half-filled shells, lowest
J has lowest energy
4. For atoms with more-than half-filled shells,
highest J has lowest energy (i.e. inverted states)

37
 Normal Multiplet
• For less than half-filled shells, smallest J lies lowest
 p2: ground term is 3P with S = 1 and L = 1
 J = 2, 1 and 0
 less than half-filled:

3P
2

3P
3P
1

3P
0
 Inverted Multiplet

• For more than half-filled shells, highest J lies lowest

 p4: ground term is 3P with S = 1 and L = 1
 J = 2, 1 and 0
 more than half-filled:

3P
0

3P
1
3P

3P
2
• The notation for a single-electron atom becomes
n2S+1 LJ
• The letters and numbers are called spectroscopic symbols.
• There are singlet states (S = 0) and triplet states (S = 1) for two electrons.

40
Ground states
Lande’s interval rule

• The form of the spin-orbit interaction energy is of the

form
Ԧ
∆𝐸𝑙,𝑠 = 𝑎(𝐿 ∙ 𝑆)
𝐽Ԧ = 𝐿 + 𝑆Ԧ
𝐽2 = 𝐿2 + 𝑆 2 + 2𝐿 ∙ 𝑆Ԧ
1 2
𝐿 ∙ 𝑆Ԧ = ℏ J J + 1 − L L + 1 − S S + 1
2
• In a given multiplet L and S are same, therefore,
∆𝐸𝐽+1 − 𝐸𝐽 = 𝐴 𝐽 + 1 𝐽 + 2 − 𝐽 𝐽 + 1 = 2𝐴(𝐽 + 1)
• Thus the energy interval between consecutive J and J+1
levels of a fine-structure multiplet is proportional to J+1, i.e.,
to the larger of the two J values involved. This is Lande’s
interval rule.
Types of coupling
• LS coupling: electron-electron » spin-orbit
        
• light elements L  l1  l2  ..., S  s1  s2  ..., J  LS
• jj coupling: spin-orbit » electron-electron
        
• heavy elements j1  l1  s1 , j2  l2  s2 , ... J  j1  j2  ...
• 2s2p: (2s1/2,2p1/2) or (2s,2p-)
• 3d5: ((3d-3)5/2,(3d+2)2)3/2
• Intermediate coupling: neither is stronger
• Other types of couplings exist
J = L+S, L+S-1,..., |L-S|
jj- coupling
Configuration sp: LS coupling (LSJ)
M
1P 1P
1
+1
-1 0
+G1

sp electro- spin- magnetic

static orbit field

3P
-G1 3P
2
+1 +2
-1 0
3P -2
1 +1 0
-1
0
3P
0

terms levels states

Configuration sp: jj coupling M

(1/2,3/2)1 +1
-1 0
(1/2,3/2)
(1/2,3/2)2
+1 +2
-1 0

-2
sp spin- electro- magnetic
orbit static field
(1/2,1/2)1

(1/2,1/2) +1 0
-1
(1/2,1/2)0
0

terms levels states

Problem
• Measurements made on the line spectrum emitted
by a certain atom of intermediate Z show that the
separations between adjacent energy levels of
increasing energy, in a particular multiplet, are
approximately in the ratio 3 to 5. Use the Landé
interval rule to assign the quantum numbers S, L, J
to these levels. This example gives some insight
into the procedure used by the experimental
spectroscopist in analyzing his measurements.