M.

Sc Chemistry 2020 - CHEM 412 : UNIT II

Atomic Structure
Of Many Electron Atoms
Musiri M. Balakrishnarajan
Chemical Information Sciences
Pondicherry University.
 Indistinguishability of Quantum Particles
For Helium atom in its excited State 1 r12
1 1 1 𝑧 𝑧 1
2
Hamiltonian: 𝐻=− ∇2𝑎 − ∇12 − ∇22 − − +
2𝑚𝑎 2 2 𝑟1 𝑟2 𝑟12 r1 r2
1
The Hamiltonian is not separable. 𝐻 = 𝐻 1 + 𝐻 2 +
𝑟12
Solving using approximation methods should retain
the orbital picture for comparison across elements.
Approximate Trial Wave Function for excited state He?
ψtrial = 1𝑠 1 ∗ 2𝑠 2 or 1s(2) 2s(1)

13 32 𝑟
= 𝑒 −1 𝑟1 . (1 − 𝑟2 )𝑒 − 22 2
𝜋 𝜋
Snapshots of identically prepared He in its 1s2s state
Probability Distribution is different for electrons 1 and 2. 1
ψsymm = [1𝑠 1 ∗ 2𝑠 2 + 1s(2) 2s(1)]
But these two electrons are indistinguishable. 2
1
Our ψtrial Should not distinguish these electrons. How? ψantisymm = [1𝑠 1 ∗ 2𝑠 2 − 1s(2) 2s(1)]
2
 Electron Spin
Intrinsic Angular momentum of electron Time Line

Stern–Gerlach experiment (1922)

Wolfgang-Pauli (1922) Non classical Hidden Rotation

Ralph Kronig (1924): unpublished Results

Uhlenbeck and Goudsmit (1925) D- lines in Sodium spectra

Coupling of orbital and spin angular momentum

Spinning on its own axis? Wolfgang-Pauli (1927) Pauli Mathematical Treatment

Electron classical velocity
exceeds speed of light. Paul M. Dirac (1927) Relativistic Hydrogen

Spin has no Classical Analogue

 Electron Spin & Pauli’s Exclusion Principle
Stern–Gerlach experiment results is interpreted as multiplicity arising from half spin particles.
Orbital Angular Momentum Spin Angular Momentum
ℎ 2 ℎ 2
𝐿2 ψ = 𝑙 𝑙+1 ψ 𝑆2ψ = 𝑆 𝑆+1 ψ
4𝜋 2 4𝜋 2
ℎ ℎ 1 1
Lz ψ = 𝑚 ψ (𝑚𝑙 =- 𝑙, - 𝑙+1,…..0….. 𝑙+1, 𝑙) Sz ψ = 𝑚𝑠 ψ (𝑚 𝑙 = − , + Referred as  and 
2𝜋 2 2
2𝜋 𝑙
Multiplicity 2 𝑙 + 1 Multiplicity 2 𝑠 + 1 (The spin of the electron is ½, half-integer)
Orbitals of different 𝑚𝑙 values are Orthonormal Electrons of two 𝑚𝑠 values are orthogonal and assumed normalized.

Ground State of Helium

(1) (2) (symmetric, allowed)

1
[(1) (2) + (1) (2)] (symmetric, allowed)
(1) (2) (unsymmetric, disallowed) 2
ψtrial = 1𝑠 1 ∗ 1𝑠 2 (superposition)
(1) (2) (unsymmetric, disallowed) 1
[(1) (2) - (1) (2)](antisymmetric, allowed)
2
(1) (2) (symmetric, allowed)
Ground state of Helium is non-degenerate, implying electrons prefer Antisymmetry.
 Lithium Ground State
(1) (2) (3) (symmetric, allowed)
(1) (2) (3) (unsymmetric, disallowed)
(1) (2) (3) (unsymmetric, disallowed) Impossible to write
(1) (2) (3) (unsymmetric, disallowed) an antisymmetric
ψtrial = 1𝑠 1 ∗ 1𝑠 2 * 1s(3) (1) (2) (3) (unsymmetric, disallowed) wavefunction.
(Linear Combination)
Three electrons
(1) (2) (3) (unsymmetric, disallowed)
cannot be
(1) (2) (3) (unsymmetric, disallowed) accommodated in 1s
(1) (2) (3) (symmetric, allowed)

(Pauli’s Exclusion Principle) No two electrons in the same atom can have
For Lithium the correct trial wave function has to
identical values for all four of their quantum numbers.
involve 2s orbitals after proper anti-symmetrization. 1s(1)*1s(2)*2s(3) ( (1) (2) (3) - (1) (2) (3))
Wavefunctions must be antisymmetric with 1
+
exchange of space and spin coordinates. Ψtrial =
6 1s(1)*2s(2)*1s(3) ((1) (2) (3) - (1) (2) (3))
+
Permutation operator Pij Commutes with Hamiltonian. 2s(1)*1s(2)*1s(3)((1) (2) (3) - (1) (2) (3))

Pij ψ = ± ψ Pauli Exclusion leads to volume and concept of space

 Excited State Helium : Revisited
1 r12
1 2 1 2 2 2 1 𝟏 2
Hamiltonian: 𝐻=−
2
∇1 − ∇2 −
2 𝑟1
−
𝑟2
+
𝑟12
= 𝑯 𝟏 +𝑯 𝟐 +
𝒓𝟏𝟐
r1 r2
Trial Wave Function is a product of space part and spin part. ψ𝑡𝑟𝑖𝑎𝑙 = ψ𝑠𝑝𝑎𝑐𝑒∗ψ𝑠𝑝𝑖𝑛
𝑠 𝑎𝑠
Antisymmetrized Trial Wave Function ψ𝑎𝑠 = ψ𝑎𝑠
𝑠𝑝𝑎𝑐𝑒 ∗ψ 𝑠𝑝𝑖𝑛 (or) ψ 𝑎𝑠 = ψ 𝑠
𝑠𝑝𝑎𝑐𝑒 ∗ψ 𝑠𝑝𝑖𝑛
Indistinguishability by Quantum superposition of Excited state He:
1 1
𝑠
ψ𝑠𝑝𝑎𝑐𝑒 = [1𝑠 1 ∗ 2𝑠 2 + 1s(2) 2s(1)] ψ𝑎𝑠
𝑠𝑝𝑖𝑛 = [(1) (2) − (1) (2)] Singlet
2𝑠 2 2

𝑠
ψ𝑠𝑝𝑖𝑛 = [(1)(2)
1 𝑠 Triplet
1𝑠 ψ𝑎𝑠
𝑠𝑝𝑎𝑐𝑒 = [1𝑠 1 ∗ 2𝑠 2 − 1s(2) 2s(1)] ψ𝑠𝑝𝑖𝑛 = [(1)(2)
2 1
𝑠
ψ𝑠𝑝𝑖𝑛 = [(1) (2) + (1) (2)]
2

Average Energy excited state He: Since Hamiltonian does not depend on spin, ψ𝑠𝑝𝑖𝑛 can be ignored
 Expectation value of Energy for Excited State Helium
𝑎/𝑠 1
Antisymmetrized Trial w/f ψ𝑠𝑝𝑎𝑐𝑒 = (1𝑠 1 2𝑠 2 ± 1s(2) 2s(1))
2
𝟏 𝑎/𝑠 𝑎/𝑠
Hamiltonian: 𝑯=𝑯 𝟏 +𝑯 𝟐 + ℰ = ψ𝑠𝑝𝑎𝑐𝑒 𝐻 ψ𝑠𝑝𝑎𝑐𝑒
𝒓𝟏𝟐
1 𝟏
= 1𝑠 1 2𝑠 2 ± 1s(2)2s(1) 𝑯 𝟏 + 𝑯 𝟐 + 𝒓 1𝑠 1 2𝑠 2 ± 1s(2)2s(1)
2 𝟏𝟐

1
= ( 1𝑠 1 2𝑠 2 ± 1s(2) 2s(1) 𝑯 𝟏 1𝑠 1 2𝑠 2 ± 1s(2) 2s(1) + 1𝑠 1 2𝑠 2 ± 1s(2)2s(1) 𝑯 𝟐 1𝑠 1 2𝑠 2 ± 1s(2)2s(1) +
2
𝟏
ℰ1s 𝟏 1𝑠 1 2𝑠 2 ± 1s(2)2s(1) 𝒓 1𝑠 1 2𝑠 2 ± 1s(2)2s(1)
𝟏𝟐
1s(1)2s(2) 𝑯 𝟏 1s(1)2s(2) 1s(1) 𝑯 𝟏 1s(1) 2s(2) 2s(2)
𝟏
± 1s(1)2s(2) 𝑯 𝟏 1s(2)2s(1) 1s(1) 𝑯 𝟏 2s(1) 2s(2) 1s(2) 𝟎 1s(1)2s(2)
𝒓𝟏𝟐
1s(1)2s(2) 𝐽
± 1s(2)2s(1) 𝑯 𝟏 1s(1)2s(2) 2s(1) 𝑯 𝟏 1s(1) 1s(2) 2s(2) 𝟎
𝟏
+ 1s(2)2s(1) 𝑯 𝟏 1s(2)2s(1) 2s(1) 𝑯 𝟏 2s(1) 1s(2) 1s(2) ± 1s(1)2s(2) 𝒓 1s(2)2s(1)
𝟏𝟐
𝐾
ℰ2s 𝟏
𝟏
± 1s(2)2s(1)
𝒓𝟏𝟐
1s(1)2s(2) 𝐾
𝐽 - Coulomb integral
ℰ± = ℰ1s + ℰ2s + 𝐽 ± 𝐾 𝟏
𝐾 - Exchange integral + 1s(2)2s(1)
𝒓𝟏𝟐
1s(2)2s(1) 𝐽
 Interpreting the Energy for Excited State Helium
ℰ± = ℰ1s + ℰ2s + 𝐽 ± 𝐾
ℰ1s 1s(1) 𝐻 1 1s(1) = 1s(2) 𝐻 2 1s(2) Energy of 1s orbital of He+
ℰ2s 2s(1) 𝐻 1 2s(1) = 2s(2) 𝐻 2 2s(2) Energy of 2s orbital of He+
1 1 1𝑠 1 2 2𝑠 2 2
𝐽 1s(1)2s(2) 1s(1)2s(2) = 1s(2)2s(1) 𝑟 1s(2)2s(1) ඵ 𝑑𝑟1 𝑑𝑟2
𝑟12 12 𝑟12
Coulomb integral (Large and Positive)
1 1 [1s(1)2s(1)] [1s(2)2s(2)]
𝐾 1s(1)2s(2) 1s(2)2s(1) = 1s(2)2s(1) 1s(1)2s(2) ඵ 𝑑𝑟1 𝑑𝑟2
𝑟12 𝑟12 𝑟12
Exchange integral (Small and Positive) 𝑄𝑢𝑎𝑙𝑖𝑡𝑎𝑡𝑖𝑣𝑒𝑙𝑦 𝑎𝑔𝑟𝑒𝑒
Singlet is less stable than Triplet 𝑤𝑖𝑡ℎ 𝐸𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡.

ℰ+ Fermi heap

2𝐾

ℰ− Fermi hole
Positive Negative Positive
 Constructing antisymmetric Wavefunctions
Exchange and permutation
1s(1)1s(2)2s(3) ((1)(2)(3)-(1)(2)(3))+ 1𝑠(1)(1) 1𝑠(2)(2) 1𝑠(3)(3) 1𝑠(1) 1𝑠(2) 1𝑠(3)
ΨLi = 1s(1)2s(2)1s(3) ((1)(2)(3)-(1)(2)(3))+ 1𝑠(1)(1) 1𝑠(2)(2) 1𝑠(3)(3) 1𝑠(1) 1𝑠(2) 1𝑠(3)
2s(1)1s(2)1s(3) ((1)(2)(3)-(1)(2)(3)) 2𝑠(1)(1) 2𝑠(2)(2) 2𝑠(3)(3) 2𝑠(1) 2𝑠(2) 2𝑠(3)

Spin orbital : product of atomic orbital (spatial) multiplied by its spin i.e., 1s(1) (1)
In general, the n electron trial wavefunction over n spin orbitals (1 , 1 , … 1 ) is
represented as a n x n ‘Slater’ determinant

electrons
1 (1) 1 2 ⋯ 1 (𝑛) Spin Diagonal entries correspond to the original
Orbitals configuration and |1 (1) 2 (2) 3 (3) ….𝑛 𝑛 >
1 2 (1) 2 (2) ⋯ 2 (𝑛) short-hand notation for the determinant
Ψtrial =
𝑛! ⋮ ⋮ ⋮ Exchange of rows (or columns) correspond to
exchange of electrons (or orbitals) and reverses
𝑛 (1) 𝑛 (2) ⋯ 𝑛 (𝑛) the sign of the determinant.

If any of the rows (or columns) is equal, the determinant vanishes (linear dependency).
 Representing Atomic Orbitals in multielectron Atom
𝑛 𝑛 𝑛−1 𝑛 𝑛 𝑛
1 𝑍 1 1
The Hamiltonian for n-electron Atom: 𝐻=− ෍ −𝛻𝑖2 − ෍ −෍ ෍ = ෍𝐻 𝑖 + ෍
2 𝑟μ𝑖 𝑟𝑖𝑗 𝑟𝑖𝑗
𝑖=1 𝑖=1 𝑖=1 𝑗=𝑖+1 𝑖=1 𝑗>𝑖

Orbital Approximation: Ignoring electron-electron repulsion in formulating trial wave function.

Atomic Wavefunction : Antisymmetrized product of one-electron spin orbital |1 1 . 2 (2) ….𝑛 𝑛 >
Atomic orbitals 𝑖 are product of pseudo-hydrogenic orbitals with its spin part. 𝑖 = 𝑠𝑝𝑎𝑐𝑒 (𝑖). 𝑠𝑝𝑖𝑛 (𝑖)
Approximating 𝑠𝑝𝑎𝑐𝑒 (𝑖) with real Hydrogenic orbitals? 𝑧𝑟 𝑙 2𝑙+1 𝑧𝑟 𝑧𝑟
−( ) 𝑙
𝜓 𝑟, θ, 𝝋 = 𝐿𝑛−𝑙−1 𝑒 𝑛𝑎 𝑌𝑚 𝜃, 𝜑
They have incorrect radial exponent and clumsy. 𝑛𝑎 𝑛𝑎
(𝑧−𝑠)𝑟
− 𝑛
Simplified Recipe from Slater : 𝜓 𝑟, θ, 𝝋 = 𝑁 𝑟 𝑛𝑒𝑓𝑓 −1 𝑒 𝑒𝑓𝑓 𝑌𝑚𝑙 𝜃, 𝜑
Slater again
𝑛𝑒𝑓𝑓 = Effective Primary Quantum number (Not used much)
𝑠 = Screening Constant
𝑧 − 𝑠 = 𝑧’ or , the effective nuclear Charge.
Current Quantum mechanical calculations use multiple STOs which are in turn
expressed in terms of GTOs, variationally optimized using Hartree-Fock Theory

Slater exponents are chemically Intuitive; used extensively for understanding periodic trends.
 Closed Shell Illustration: Be
4 4
1 1
𝐻 = ෍𝐻 𝑖 + ෍ Ψtrial = |1𝑠 1 1𝑠(2)2𝑠 3 2𝑠(4) > ℰ = Ψtrial 𝐻 Ψtrial
𝑟𝑖𝑗 4!
𝑖=1 𝑗>𝑖

1𝑠 1 1𝑠 2 1𝑠 3 1𝑠 4
4!
1 1𝑠 2 1𝑠 2 1𝑠 3 1𝑠 4 1 𝑝 𝑃(1𝑠
Ψtrial = = ෍ −1 1 1𝑠 2 2𝑠 3 2𝑠 4 )
4! 4! 𝑝=1
2𝑠 1 2𝑠 2 2𝑠 3 2𝑠 4

2𝑠 2 2𝑠 2 2𝑠 3 2𝑠 4

Representative Examples of different types of product Terms

Diagonal Term: (1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 )

Singly Permuted Term: (1𝑠 1 1𝑠 4 2𝑠 3 2𝑠 2 ) (Exchange of electrons of same spin P(2,4))

Singly Permuted Term: (1𝑠 2 1𝑠 1 2𝑠 3 2𝑠 4 ) (Exchange of electrons of Different spin P(2,4))

Doubly Permuted Term: (1𝑠 2 1𝑠 1 2𝑠 4 2𝑠 3 ) (Exchange of electrons of Different spin P(2,4))

 Illustration: Li
4!
1 𝑝
Ψtrial = ෍ −1 𝑃(1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 )
4! 𝑝=1

1 4! 𝑝 1 4! 𝑝
ℰ= σ𝑝=1 −1 𝑃(1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 ) 𝐻 σ𝑝=1 −1 𝑃(1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 )
4! 4!
1
= σ4! −1 𝑝 𝑃(1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 ) 𝐻 σ4!
𝑝=1 −1
𝑝 𝑃(1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 )
4! 𝑝=1
4!
= (1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 𝐻 σ4!
𝑝=1 −1
𝑝 𝑃(1𝑠
1 1𝑠 2 2𝑠 3 2𝑠 4 )
4!

Not Necessary to evaluate all the 4! Integrals.

These integrals times their +1 or -1 coefficients are all Equal

The final Expression for energy boils down to evaluating just

ℰ = (1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 𝐻 σ4!
𝑝=1 −1
𝑝 𝑃(1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 )
 Expectation Values of H(i)
4 4
1
ℰ = (1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 𝐻 σ4!
𝑝=1 −1 𝑝 𝑃(1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 ) 𝐻 = ෍𝐻 𝑖 + ෍
𝑟𝑖𝑗
𝑖=1 𝑗>𝑖

ℰ𝐻 𝑖 = (1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 σ4𝑖=1 𝐻 𝑖 σ4!

𝑝=1 −1
𝑝
𝑃(1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 )

Still 4 x 4! Terms, out of which only four terms will be having LHS and RHS equal, one for each electron.

For Example, ℰ𝐻 1 = (1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 𝐻(1) 1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4

= (1𝑠 1 𝐻(1) 1𝑠 1 1𝑠 2 1𝑠 2 2s(3) 2s(3) 2𝑠 4 2𝑠 4
= ℰ1𝑠
Other 4 (4! -1) terms will vanish because of orthogonality irrespective of the operator
ℰ𝐻 1 = (1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 𝐻(1) 1𝑠 2 1𝑠 1 2𝑠 3 2𝑠 4

= (1𝑠 1 𝐻(1) 1𝑠 1 1𝑠 2 1𝑠 2 2s(3) 2s(3) 2𝑠 4 2𝑠 4

In total We have ℰ𝐻 𝑖 = 2ℰ1𝑠 + 2ℰ2𝑠

 Expectation Values of electron-electron Interaction
1
ℰ𝑒−𝑒 = (1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 σ4𝑗>𝑖 σ4!
𝑝=1 −1
𝑝
𝑃(1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 )
𝑟𝑖𝑗

Still 6 x 4! Terms, only those integrals involving zero and one permutation remains. For Example,
1 1
0: (1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 𝑟 1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 = 1𝑠 1 1𝑠 2 = 𝐽1𝑠1𝑠
𝑟12 1𝑠 1 1𝑠 2 2s(3) 2s(3) 2𝑠 4 2𝑠 4
12

1 1
𝑃12: (1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 𝑟 1𝑠 2 1𝑠 1 2𝑠 3 2𝑠 4 = 1𝑠 1 1𝑠 2 𝑟 1𝑠 2 1𝑠 1 2s(3) 2s(3) 2𝑠 4 2𝑠 4
12 12

1
Exchange between different spins disappear 1𝑠 1 1𝑠 2 𝑟 1𝑠 2 1𝑠 1 (1) (1) (2) (2) = 0
12
1 1
𝑃13: (1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 𝑟 1𝑠 3 1𝑠 2 2𝑠 1 2𝑠 4 = 1𝑠 1 2𝑠 3 𝑟 1𝑠 3 2𝑠 1 1𝑠 2 1𝑠 2 2𝑠 4 2𝑠 4 = 𝐾1𝑠2𝑠
13 13

1 1
𝑃34: (1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 𝑟 1𝑠 1 1𝑠 2 2𝑠 4 2𝑠 3 = 1𝑠 1 1𝑠 2
12 𝑟12 1𝑠 1 1𝑠 2 2𝑠 3 2s(3) 2s(4) 2𝑠 4 =0

1 1
𝑃12,34: (1𝑠 1 1𝑠 2 2𝑠 3 2𝑠 4 𝑟 1𝑠 2 1𝑠 1 2𝑠 4 2𝑠 3 = 1𝑠 1 1𝑠 2 𝑟 1𝑠 1 1𝑠 2 2𝑠 3 2s(3) 2s(4) 2𝑠 4 = 0
12 12
4 4

= 𝐽1𝑠1𝑠 + 𝐽1𝑠2𝑠 + 𝐽1𝑠2𝑠 + 𝐽1𝑠2𝑠 + 𝐽1𝑠2𝑠 + 𝐽2𝑠2𝑠 −𝐾1𝑠2𝑠 − 𝐾1𝑠2𝑠 = ෍ ෍ 2𝐽𝑖𝑗 − 𝐾𝑖𝑗
𝑖=1 𝑗=1
 Energy of multielectron Atom
𝑛 𝑛
1
𝐻𝑎𝑚𝑖𝑙𝑡𝑜𝑛𝑖𝑎𝑛 𝐻 = ෍ 𝐻 𝑖 + ෍
𝑟𝑖𝑗
𝑖=1 𝑗>𝑖

|1 1 1 (2)2 3 2 (4) … 𝑛 2𝑛 − 1 𝑏 (2𝑛) > where  = 𝑁 𝑟 𝑛 𝑒 −𝑟 𝑌𝑚𝑙 𝜃, 𝜑

1
Ψtrial =
2𝑛!

ℰ = Ψtrial 𝐻 Ψtrial
For a Closed Shell System
𝑛 𝑛 𝑛

ℰ = Ψ2n 𝐻 Ψ2n = 2 ෍ 𝐻𝑖𝑖 + ෍ ෍ 2𝐽𝑖𝑗 − 𝐾𝑖𝑗

𝑖=1 𝑖=1 𝑗=1

𝐻𝑖𝑖 = 𝑖 𝑎 𝐻(𝑎) 𝑖 𝑎 Physicist Chemist

1
𝐽𝑖𝑗 = 𝑖 𝑎 𝑗 (𝑏) 𝑖 𝑎 𝑗 𝑏 = 𝑖𝑗 𝑖𝑗 = 𝑖𝑖 𝑗𝑗 Coulomb integral
𝑟𝑎𝑏

1
𝐾𝑖𝑗 = 𝑖 𝑎 𝑗 (𝑏) 𝑖 𝑏 𝑗 𝑎 = 𝑖𝑗 𝑗𝑖 = 𝑖𝑗 𝑖𝑗 Exchange integral
𝑟𝑎𝑏

For Open Shell systems, a generic expression for energy is not available.
 Multielectron atoms:: Various Approximations
The Hamiltonian Operator 𝑛 𝑛 𝑛−1 𝑛 𝑛
electronic Schrodinger 1 𝑍 1
𝐻𝑒𝑙𝑒𝑐 = − ෍ 𝛻𝑖2 − ෍ + ෍ ෍ 𝐻𝑒𝑙𝑒𝑐 ≠ ෍ 𝐻(𝑖)
2 𝑟𝑖 𝑟𝑖𝑗
equation cannot be 𝑖=1 𝑖=1 𝑖=1 𝑗=𝑖+1 𝑖=1

separated.
Inter-electron Repulsion
From Ψ𝑆𝑇𝑂 = 𝑅𝑛,𝑙 𝑟 . 𝑌𝑙,𝑚 𝜃, 𝜑 , energy obtained ℰ = ΨSlater 𝐻 ΨSlater is only qualitative.

Trial wave functions with varying parameter  for the same orbital.
Further Improvement? Trial wave functions with varying  that breaks product type orbitals.
Methods that vary the trial wave functions itself, not just parameters.
Ψ𝑇𝑟𝑖𝑎𝑙 = 1 𝑟1 , 𝜃1 , 𝜑1 2 𝑟2 , 𝜃2 , 𝜑2 1 𝑟3 , 𝜃3 , 𝜑3 …… n 𝑟𝑛 , 𝜃𝑛 , 𝜑𝑛

Look for wave functions 1 , 2 , 3 …that minimize the variational

integral. These are not necessarily hydrogenic orbitals.

Radial –Angular Separation can be still used. i 𝑟𝑖 , 𝜃𝑖 , 𝜑𝑖 = ℎi 𝑟𝑖 , 𝜃𝑖 , 𝜑𝑖 , Ylm 𝜃1, 𝜑1

 Hartree Operator
Product type Ψ𝑆𝑇𝑂 = 1 𝑟1 , 𝜃1 , 𝜑1 2 𝑟2 , 𝜃2 , 𝜑2 …… n 𝑟𝑛 , 𝜃𝑛 , 𝜑𝑛
𝑛−1
Electron-Electron interaction is computed as the 𝑞1 ψ2𝑗
𝑉𝑖𝑗 𝑖 = න 𝑑𝑟𝑗 𝑉𝑒𝑒 𝑖 = ෍ 𝑉𝑖𝑗(𝑖)
average potential arising from the other electron. 4π𝜖0 𝑟𝑖𝑗
𝑖≠j

Modified total energy operator 𝑛 𝑛 𝑛−1

1 𝑍
that allows separation is defined 𝑯 = − ෍ −𝛻𝑖2 − ෍ + ෍ 𝑉𝑒𝑒(𝑖) 𝑟𝑖 Average Repulsion
2 𝑟𝑖
by Hartree (1928) using Mean Field 𝑖=1 𝑖=1 𝑖=1

Approximation.
𝑧
Effective Potential is assumed to be 𝑉𝑖 𝑟1 , 𝜃1 , 𝜑1 = 𝑉𝑒𝑒 𝑖 −
𝑟𝑖
a function of r only by averaging 𝜋 2𝜋
over the angles ‫׬‬0 ‫׬‬0 𝑉𝑖 𝑟𝑖 ,𝜃𝑖 ,𝜑𝑖 sin 𝜃𝑖 d𝜃𝑖 d𝜑𝑖
𝑉𝑒𝑒(𝑖) 𝑟𝑖 = 𝜋 2𝜋
(Central Field Approximation) ‫׬‬0 ‫׬‬0 sin𝜃 d𝜃d𝜑

This reduces the n-electron equation to 1

− 𝛻𝑖2 + 𝑉𝑖 𝑟𝑖 ψ𝑖 = ℰi ψ𝑖 n = l + 1 + k, k = 0,1,2….
one electron Schrodinger equation. 2
𝑛 𝑛
Since Hamiltonian is separable, wave functions are product of
𝐇𝑒𝑙𝑒𝑐 = ෍ 𝑯(𝑖) Ψtrial = ෑ ψ𝑖
one-electron functions. (Similar n-l-1 radial nodes)
𝑖=1 𝑖
Hartree Operator :: Self-Consistent Field Approximation
𝑛
Mean Field is the interaction of the ψ2𝑗
𝑉𝑒𝑒(𝑖) = ෍ න
electron with the average potential arising 𝑗≠𝑖
𝑟𝑖𝑗
from all other electrons independently.
This requires information about the one electron function ψi that
need to be supplied as a trial wave function.
To Start with, an initial guess wave function is generated and is used to construct
the necessary one electron operators including electron-electron repulsion.
Numerical Solutions to each equations hiψi = Eiψi give a new and presumably better ψi .

The one electron Hamiltonian operators (hi) are constructed anew from the improved ψi
This entire process is repeated till the initial and final densities are same.
The converged iterative process leads to self-consistency of the effective field.
Total Energy is not a sum of individual one electron energies as they are counted twice.
 Hartree-Fock Method : Introducing Antisymmetry
Hartree’s Product type wave function lacks spin and defies Pauli’s Antisymmetry.
Replaced with the antisymmetrized product for fermions (half-integer spin).
Antisymmetrized Products are from Slater Determinants.
1
|1 1 1 (2)2 3 2 (4) … 𝑛 2𝑛 − 1 𝑏 (2𝑛) >
2𝑛!
For a closed Shell system, the variational method leads to Fψi= Eiψi, F → Fock Operator
𝒏 𝑛 𝑛 𝑛
1 2 𝑍
𝑭 = ෍𝐹 𝑖 𝐹 𝑖 = − ෍ 𝛻𝑖 − ෍ + ෍ 2𝐽𝑗 − 𝐾𝑗
2 𝑟𝑖
𝒊=𝟏 𝑖=1 𝑖=1 𝑗=1

Coulomb 𝐽𝑗 = න Ψj(2)∗ (1/𝑟12 )Ψj(2) 𝑑τ2 Exchange 𝐾𝑗 Ψj(1) = න Ψj(2)∗ (1/𝑟12 )Ψi(2) 𝑑τ2 Ψj(1)
Operator Operator
Problems?: Double counting Electron Correlation

Correlation Energy : ℰ𝐻𝐹 – True Energy. Solution: Configuration Interaction (Multiple Determinants )
 HF-SCF Theory : Nature of Solutions
One Electron Energies 𝐸𝑖 = 𝐻𝑖𝑖 + σ𝑛𝑗=1 2𝐽𝑖𝑗 − 𝐾𝑖𝑗

Sum of Average kinetic energy and electron nuclear attraction energy of electron in ψi

Atomic total energies are corrected The Energy of the electron in the kth MO is the
for double counting (Closed Shell). Ionization Energy of that electron (Koopman Theorem)
𝑛 𝑛
Ionization Energy kth orbital E(n) –E(n-1)
𝐸𝑒𝑙𝑒𝑐 = ෍ 2𝐸𝑖 − ෍ 2𝐽𝑖𝑗 − 𝐾𝑖𝑗
𝑖=1 𝑗=1 𝐼. 𝐸 = ψ1 . ψ2 … . ψ𝑘 . ψ𝑘+1 … ψ𝑛 𝐻 ψ1 . ψ2 … . ψ𝑘 . ψ𝑘+1 … ψ𝑛 −
Hence ψ1 . ψ2 … . ψ𝑘+1 . ψ𝑘−1 … ψ𝑛 𝐻 ψ1 . ψ2 … . ψ𝑘+1 . ψ𝑘−1 … ψ𝑛
𝑛 𝑛

𝐸𝑒𝑙𝑒𝑐 = ෍ 2𝐻𝑖𝑖 + ෍ 2𝐽𝑖𝑗 − 𝐾𝑖𝑗

𝑖=1 𝑗=1
= ψ𝑘 𝐻 ψ𝑘
𝑛

= ෍ 𝐸𝑖 + 𝐻𝑖𝑖 = 𝐸(𝑘)
𝑖=1
 Hartree-Fock SCF Method
Slater Determinantal wave functions are not unique. Using a single Slater
determinantal wave function is restrictive.
Errors associated with the usage of single determinantal wave-function is
generally referred as ‘electron correlation’. This usage unfortunately emphasizes
the particle nature of electron.
There is some built-in Electron correlation referred as “Fermi correlation” accounted
within the HF-SCF method.
Multi-determinantal wave functions address the error associated with HF-SCF method
but lacks physically meaningful interpretation.
Presence of unpaired electron require modification, I.e., UHF or ROHF.
Numerical nature of the solutions renders HF-SCF wavefunctions though more accurate
unhelpful in analysis. Slater type Orbitals, though inaccurate in their nodal features, are
extremely useful in understanding trends.
 The Aufbau Principle
Aufbau (Building up) Principle by Bohr & Pauli (1921)
Elliptic Orbits of Old Quantum Theory

5p l = 4
5p l = 3
5p l = 2
5p l = 1
5s l = 0
Niels Bohr Wolfgang Pauli

Highest Angular momentum implies circular orbits – Far away from the nucleus – More Screening

Highest Eccentricity corresponds to smaller l values – Close to the nucleus – More penetration.
 Breaking of n2 Degeneracy: Penetration and Screening
(𝑧−𝑠)𝑟
𝑛−1 −
Slater Type Orbital 𝜓 𝑟, θ, 𝝋 = 𝑁 𝑟 𝑒 𝑛 𝑌𝑚𝑙 𝜃, 𝜑
Screening Constants: 1s-1s : 0.30 ns-ns, np-np : 0.35 n-(n-1): 0.85 n-(n-2) : 1.0 n-(n+1): 0.0

Penetration : s > p > d > f > g

Screening from n-1 to n
7p
6d 5f 7s 7p 7d 7f Primogenic Effect
7s 6p
5d 4f sp gap
6s 6p 6d 6f
6s 5p increases across rows
4d reduces across columns
5s 5s 5p 5f
4p 5d Relative Diffuseness of s and p
3d
4s Decreases across Row
4s 4p 4d 4f Increases across columns
3p
3s 3s 3p 3d Origin of
Diagonal Relationship
2p
2s 2s 2p Inert Pair Effect
Variable Valences
1s
1s Lanthanide Contraction
Radial Distributions
 Ionization Energies
1st Ionization Energies
increases along rows
decreases with columns
Successive ionization
reveals the
Shell Structure
 Atomic Radius (Empirical)
Defining Atomic Radius is hard, Usually the spherical approximation is made.
Several measures (ionic, covalent, van-der walls and metallic) exists for different situations.
Smallest Hydrogen & Fluorine
Increases across columns
Across Rows S > P > D

Corey, Pauling & Koltun Empirical Radius (Slater)

Space
Filling
Model
 Fine Structure of Atoms
Includes magnetic Interactions from electrons. (from Orbital motion and spin )
Experimental spectral patterns (absorption and emission) reveals fine structure.
Arising from the coupling of orbital and spin angular momentum
l and s are not independently conserved (not good quantum numbers.)
The total angular momentum J , the vector sum of orbital and spin angular momentum, is conserved.
SZ

J=L+S

J2 = L2 + S2 +2 L. S

L.S = ½ (J2 - L2 - S2)

< J2 > = ½ J (J+1)

< Jz > = mj, mj = -J, -J+1, … 0… J-1, J

Dirac Relativistic Model

Treatment of Spin-Orbit coupling:
Perturbation theory
 Spin-Orbit Coupling for Hydrogenic systems
2s+1 2s+1 2s+1 𝑚𝑗 𝑙 value 0 1 2 3 4
Representation 𝑙 𝑙𝑗 𝑙𝑗 Symbol s p d f g
State Term Microstate
Split by Exchange Integral spin-Orbit Coupling External magnetic field

Configuration Orbital l Spin s Total j Length Term Multiplicity

2
Ground State 1s1 0 1/2 1/2 3/2 𝑠1/2 2
Couple the LARGE
2
Excited State 2s1 0 1/2 1/2 3/2 𝑠1/2 2 valued Angular
momentum
2
𝑝3/2 4 component with all
Excited State 2p1 1 1/2 3/2 15/2
possible values of
2 the smaller
1 -1/2 1/2 3/2 𝑝1/2 2 component
2
Excited State 3d1 2 +1/2 5/2 35/2 𝑑5/2 6
2
2 -1/2 3/2 15/2 𝑑3/2 4
The orbital value of l is coupled with both parallel and antiparallel spins to arrive at the terms
 Coupling in Multi-electron Atoms
Qualitative Treatment of Spin-Orbit coupling:
Lighter atoms : L-S coupling (Russell-Sanders)
Couple the orbital component of angular momentum of individual electrons l to form L

Couple the spin component of angular momentum of individual electrons s to form S

Couple the various possibilities of L and S to arrive at J.

2S+1 2S+1 2S+1 𝑚𝑗 𝑙 value 0 1 2 3 4

Representation 𝐿 𝐿𝑗 𝐿𝑗 Symbol S P D F G
State Term Microstate

Heavier atoms : J-J coupling

Couple the orbital and spin component of every electrons to form j

Couple the j vectors of all electrons to form J

 Russell Sanders Coupling
s orbitals do not have orbital angular momentum
In completely filled subshells, the total orbital component and spin component cancel each other
Enough to Consider only partially filled sub-shells.
Example: Carbon in the configuration 1s2 2s2 2p13p1 1s2 2s2 2p2
For every Possible value of L, Pauli violation
Max Orbital component ml = 1 Couple with all possible values of S Similarity
Possible coupling of Orbital components L S J Term reduces the
of the other electron L = 2, 1, 0 possibilities
3𝐷
-1 0 1 3 3
L=0
2 1 2 3𝐷
2 Not Possible with 2p2
3𝐷
1 1
L=1 1𝐷
2 0 2 2
3𝑃
L=2 2 2
3𝑃
1 1 1 1
3𝑃
Max spin component ms = ½() 0 0
1𝑃
Possible coupling of spin components S = 1 ( ,), 0 ( ,) 1 0 1 1 Not Possible with 2p2

1 1 3𝑆 Not Possible with 2p2

0 1
1𝑆
0 0 0 0
 Hund’s Rules
(1) S: For a given configuration, Terms with higher multiplicity are more stable
Due to Pauli Exchange, terms with higher multiplicity have lesser repulsion than those with lower multiplicity.
Also Referred to as “Hund’s Rule of maximum multiplicity”
(2) L : For a given multiplicity, Terms with higher L values are more stable.
Electrons with higher L are orbiting in the same direction, possibly avoiding frequent close encounters.

(3) J : For a given L and S

For less than half filled subshells, terms with lower J values are more stable.
For more than half filled subshells, terms with higher J values are more stable.

Spin orbit coupling, i.e., the L-S interaction energy changes sign for more than half filled shells

These are empirical rules and has exceptions. Applicable only for Ground State predictions.