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CHEM F111 General Chemistry Lecture 09

Many electron atoms
 Review of lecture 08

• Hydrogenic atom: probability density and radial

probability distribution
• Hydrogen atom: Selection rule for electronic spectra
• Orthogonality and orthonormality
• Many-electron atoms – Hamiltonian operator
• Pauli principle and anti-symmetry
• Orbital approximation, spin-orbitals
• Wavefunctions for high-spin and low-spin states
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Many electron atoms (revision)

Hamiltonian:
2 2 2 2 2
ℏ 2 ℏ 2 2 Ze Ze e
− ∇N− ( ∇ 1 + ∇ 2 +…)− − −…+ +…
2 mN 2 me 4 π ϵ 0 r 1 4 π ϵ0 r 2 4 π ϵ0 r 12
(K.E)N (K.E.)e VNe Vee

According to Pauli principle, the wavefunction of a many-electron system

must be anti-symmetric with respect to interchange of the coordinates of any
two electrons.
ψ( x̄ 1 … x̄ i −1 , x̄ i , x̄ i +1 … x̄ j −1 , x̄ j , x̄ j +1 … x̄ n )=−ψ( x̄ 1 … x̄ i −1 , x̄ j , x̄ i+1 … x̄ j−1 , x̄ i , x̄ j +1 … x̄ n )

x̄≡{⃗r , spin}

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Anti-symmetry in electronic states:
(revision)

Thus, the valid wavefunctions are:

1
ψs ( x̄ 1 , x̄ 2 )= N spatial , s [ϕ i ( ⃗r 1 )ϕ j ( ⃗r 2 )+ϕ j ( ⃗r 1 ) ϕi ( ⃗r 2 )][α(1)β(2)−β(1)α (2)]
√2
ψt ( x̄1 , x̄ 2 )( M S = 1)= N spatial , t [ϕi ( ⃗r 1 ) ϕ j ( ⃗r 2 )−ϕ j ( ⃗r 1 ) ϕi ( ⃗r 2 )]α(1)α (2)
1
ψt ( x̄1 , x̄ 2 )( M S = 0)= N [ϕ ( ⃗r )ϕ ( ⃗r )−ϕ j ( ⃗r 1 )ϕi ( ⃗r 2 )][α(1)β(2)+β(1) α(2)]
√ 2 spatial , t i 1 j 2
ψt ( x̄1 , x̄ 2 )( M S =−1)= N spatial ,t [ϕ i (⃗r 1 )ϕ j (⃗r 2 )−ϕ j (⃗r 1 )ϕi (⃗r 2 )]β(1)β(2)
Hamiltonian does not depend on the electron spin, and the energy would depend only on the
spatial part of the wavefunctions. Thus, there is only one state corresponding to the anti-
symmetric spin arrangement and is called singlet. There are three states (same spatial part,
same energy) corresponding to symmetric spin arrangements and thus form a triplet.
What happens to the singlet and triplet wavefunctions when the two electrons approach each
other?
In triplet state, the wavefunction vanishes when the electrons approach each other, thereby,
effectively reducing the electron-electron repulsion. Thus, the energy of a high-spin state is
lowered as compared to the corresponding low-spin state.

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Orbital approximation: He atom

The orbital approximation allows us to express the electronic structure of an atom

in terms of its configuration, the list of occupied orbitals.
For example, we ignore the inter-electronic repulsion, the ground state
wavefunction of He could be written as
ψspatial(1,2) = (8/πa03)1/2exp(-2r1/a0)(8/πa03)1/2exp(-2r2/a0)

1 8
ψ( x̄ 1 , x̄ 2 )=
( ) 3
√ 2 π a0
e
2(r + r )/ a
1 2 0
[α(1)β(2)−β(1)α(2)]

corresponding to the configuration 1s2, with the 1s orbital being somewhat more
compact than in H.
What about Li? (Can all 3 electrons occupy 1s orbital ?)

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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,
S=0 hence, MS=0).
=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?
2p
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Shielding

In a many electron atom, each electron is shielded from the nucleus by the
others, and to a first approximation, each electron may be thought of as
experiencing an effective nuclear charge (which is less than the actual
nuclear charge).

The effective nuclear charge experienced by an electron will be determined

by its probability density distribution, and this in turn by its wavefunction.

Electrons in s-type orbitals shield more effectively than the ones in p-type,
d-type,... orbitals.

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Penetration

The radial probability distribution function for s-type orbitals is

greater than the p-, d-, etc type orbitals of the given shell.

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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.
In turn, the effective nuclear charge experienced by the ‘p’ electron will be
greater than that for a ‘d’ electron in the same shell. 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 sub-shells 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 up to
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 6C2 = 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: The spin and orbital angular momenta of electrons and the
coupling between the two – 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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Spin and orbital angular momenta:
Interaction energy

l HIGH ENERGY
Magnetic moments are
parallel (angular momenta
are parallel)
s

l LOW ENERGY
Magnetic moments are
s antiparallel (angular
momenta are antiparallel)

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: Vectors Case: Vectors
Case: Vectors
aligned oppositely differently
aligned in same
aligned
direction

|⃗J |=|L
⃗ |+|⃗S | |⃗J |=|L S|
⃗ |−|⃗ |L
⃗ |−|⃗S |≤|⃗J |≤|L
⃗ |+|⃗S |
⃗S
⃗S ⃗S
L
⃗ L
⃗

L
⃗ ⃗J ⃗J
⃗J

Components of vectors add like scalars.

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Spin orbit coupling

Energy of the spin-orbit coupling is given by:

E spin−orbit ∝ [ j ( j+1)−l (l +1)−s( s+1)]

E spin−orbit = c spin−orbit [ j ( j+1)−l (l +1)−s( s+1)]

For a single electron, s= ½;

If the electron is in s-type orbital, then orbital angular momentum is zero;

thus, 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 of the
electron corresponding to the total angular momentum of the
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 and Saunders who
introduced it)

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Terms and levels (in LS coupling)

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 orbital angular momentum quantum number (L) and
total spin angular momentum quantum number (S), the term is
represented by term symbol of the form:

(spectroscopic symbol for L)

2S+1

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,

S=s and consequently,
there is only one term. For L=l=0,
L=l=0 there is only one level with
J=S=s;
J=S=s whereas, for L>0,
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;
=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)
S=1 and a singlet (S=0),
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: Electrons in different sub-
shells

Terms and levels for e.c. 1s22s22p13p1?

L = 2,1,0;
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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