M.

Sc Chemistry 2021-22 - CHEM 412 : UNIT V

Electronic Structure
Of Molecules
Musiri M. Balakrishnarajan
Chemical Information Sciences
Pondicherry University.

"Attempts to regard a molecule as consisting of specific atoms or ionic units held together by
discrete numbers of bonding electrons or electron pairs are considered as more or less meaningless."
-Robert Mulliken (1932).
 Molecular Wavefunction
Sources of Energy in the molecule?
Etotal = Eelectronic + E vibrational + ERotational + E translational

𝑚 𝑚
~Ratio 1 : : : Free
𝑀 𝑀

Are they strictly Separable?

Separability of Hamiltonian: If Htotal = Helectronic + Hvibrational+ Hrotational + Htranslational

Schrodinger’s Hamiltonian
Mixed Terms
Nuclear Terms
𝑁 𝑛 𝑁 𝑛 𝑛 𝑁
1 1 𝑍𝜇 1 1
𝐻 = − 𝛻𝜇2 + − 𝛻𝑘2 + − + + + +
2𝑚𝜇 2𝑚𝑘 𝑟𝜇𝑘 rij 𝑅𝑎𝑏
𝜇=1 𝑘=1 𝜇=1 𝑘=1 𝑖𝑗 𝜇,𝛾

Electron Term
 H2+ Molecule : The Schrodinger Equation
1
The Hamiltonian
rA1 rB1
H = T (Kinetic Energy) + V (Potential Energy)
A B 1 1 1 2 1 1 1
RAB 𝐻= − 2
𝛻 − 2
𝛻 − 𝛻1 − − +
2𝑚𝑎 𝑎 2𝑚𝑏 𝑏 2 𝑟1𝑎 𝑟1𝑏 𝑅𝑎𝑏

Three Body Problem : Closed from of Solutions does not exist

Separation of Variables: If Htot = H1 + H2, than Etot = E1 + E2 and tot = 1 * 2

Separation of Nuclear and Electronic parts of the Hamiltonian

Nuclear Terms

1 1 1 1 1 1
𝐻= − 𝛻𝑎2 − 𝛻𝑏2 − 𝛻12 − − +
2𝑚𝑎 2𝑚𝑏 2 𝑟1𝑎 𝑟1𝑏 𝑅𝑎𝑏

Electron Term Mixed Terms

 H2+: Molecule: Bonn-Oppenheimer Approximation
Total = Nuclear * Electronic

Justification : electron Mass << Proton mass (1836 times)

First Step : Freeze the Nuclei and Solve for Electronic Schrodinger equation
𝐻𝑒𝑙𝑒𝑐 (𝑟, 𝑅)𝑒𝑙𝑒𝑐 (𝑟, 𝑅) = 𝐸𝑒𝑙𝑒𝑐 𝑟, 𝑅 𝑒𝑙𝑒𝑐 (𝑟, 𝑅
1 2 1 1 1
𝐻𝑒𝑙𝑒𝑐 = − 𝛻1 − − +
2 𝑟1𝑎 𝑟1𝑏 𝑅𝑎𝑏

Second Step : Solve the nuclear Schrodinger Equation using Eelec as potential energy
1 1
𝐻𝑛𝑢𝑐𝑙 = − 2
𝛻𝑎 − 𝛻𝑏2 + 𝑉𝑒𝑙𝑒𝑐
2𝑚𝑎 2𝑚𝑏
BO approximation leads to the concept of Potential energy surface (PES)
justifies Molecular Structure as the Equilibrium geometry (minimum on the PES)
 H2+: Molecule: Solving the Electronic Schrodinger Equation
1 2 1 1 1
𝐻𝑒𝑙𝑒𝑐 = − 𝛻1 − − + Coordinate System?
2 𝑟1𝑎 𝑟1𝑏 𝑅𝑎𝑏
Elliptical Coordinate System
λ = (rA1 + rB1 )/ R (Ellipse, 1 to ∞)
μ = (rA1 - rB1 )/ R) (Hyperbola, -1 to +1)
φ = Angle to the axis (Circle, 0 to 2π)
𝑒𝑙𝑒𝑐 𝑟A 1, 𝑟𝐵1 , 𝑅 = F(λ) . S(μ). Φ (φ)
F(λ) and S(μ) cannot be solved Analytically,
Only numerical solutions possible.
Φ(φ) part is Particle in a ring. No Energy Component.
The solutions are Aeimφ where m = 0, 1, 2, ….etc.
L2 does not commute with H, but Lz does. (, π, δ..etc.)
Electronic Total energy fitted as a function of R, is used for solving nuclear Schrodinger equation
 H2+ Molecule: Variational Solutions
𝐻𝑎𝑎 − 𝐸𝑆𝑎𝑎 𝐻𝑎𝑏 − 𝐸𝑆𝑎𝑏 𝐶1 𝐻𝑎𝑎 = Hbb = -ve
1 Secular
=0
Determinant 𝐻𝑏𝑎 − 𝐸𝑆𝑏𝑎 𝐻𝑏𝑏 − 𝐸𝑆𝑏𝑏 𝐶2 𝑆𝑎𝑎 = 1; 𝑆𝑎𝑏 = S
rA1 rB1
𝐻𝑖𝑗 = < 1𝑠𝑖 𝐻 1𝑠𝑗 > 𝑆𝑖𝑗 =< 1𝑠𝑖|1𝑠𝑗 >
A B 1
RAB 𝐻𝑎𝑎  𝐻𝑎𝑏  = (1𝑠𝑎  1𝑠𝑏 )
Solutions 𝐸 =
1  𝑆𝑎𝑏 2(1  𝑆𝑎𝑏 )
Hamiltonian 1
σU
𝐸− +
Haa-Hab 𝑅
1 1 2 1 1
𝐻= − − 𝛻1 − + 1Sa 1Sb
EH
𝑟𝑎1 2 𝑟𝑏1 𝑅𝑎𝑏 -0.5 𝐸+ +
1
𝑅
σg
E-
1sa 1sb
-1.0
Trial Wave Function Haa
E+ Stabilization of σg
 𝑇𝑟𝑖𝑎𝑙 = 𝐶1 1𝑠𝑎 (1) + 𝐶2 1𝑠𝑏 (1) less than
Linear Combination Avoids Distinguishability Destabilization OF σU
-1.5 WHY?
Resonance (H+…H + H…H+) Haa+Hab
 H2 Molecule: Trial Wave Functions
1 rb1
b Hamiltonian & its Partitioning
ra1 Rab rb2 1 1 1 1 1 1 1 1
𝐻 = − 𝛻12 − − 𝛻22 − − − + +
2 𝑟1𝑎 2 𝑟2𝑏 𝑟2𝑎 𝑟1𝑏 𝑟12 𝑅𝑎𝑏
a ra2 2

Atomic Partitioning : Resonance Structures Molecular Partitioning : Molecular Orbitals

1 1 1 1 1 1 1 1 1 2 1 1 1 2 1 1 1 1
𝐻 = − 𝛻12 − − 𝛻22 − − − + + 𝐻 = − 𝛻1 − − − 𝛻2 − − + +
2 𝑟1𝑎 2 𝑟2𝑏 𝑟2𝑎 𝑟1𝑏 𝑟12 𝑅𝑎𝑏 2 𝑟1𝑎 𝑟1𝑏 2 𝑟2𝑏 𝑟2𝑎 𝑟12 𝑅𝑎𝑏
Ha(1) Hb(2) 𝐻2+ (1) 𝐻2+ (2)

 𝑇𝑟𝑖𝑎𝑙 = 𝐶1 . 1𝑠𝑎 1 . 1𝑠𝑏 2  𝑇𝑟𝑖𝑎𝑙 = 1𝑠𝑎 1 + 1𝑠𝑏 1 ∗ (1𝑠𝑎 2 + 1𝑠𝑏 2 )

Distinguishable: Avoided by Linear combination
 𝑇𝑟𝑖𝑎𝑙 = σ𝑔 1 . σ𝑔 2
 𝑇𝑟𝑖𝑎𝑙 = 𝐶1 . 1𝑠𝑎 1 . 1𝑠𝑏 2  𝐶2 . 1𝑠𝑎 2 . 1𝑠𝑏 1
Not Distinguishable:
Coupling with spin and Anti-symmetrization
1
Coupling with spin and Anti-symmetrization
Singlet : (α 1 β 2 − (α 2 β 1
2 1
1 Singlet : (α 1 β 2 − (α 2 β 1
Triplet : (α 1 β 2 + (α 2 β 1 , α 1 α 2 , β 1 β 2 2
2
 H2 Molecule: Heitler – London Model (1927)
Trial Wave Function  𝑇𝑟𝑖𝑎𝑙 = 𝐶1 1𝑠𝑎 1 1𝑠𝑏 (2) + 𝐶2 1𝑠𝑎 2 1𝑠𝑏 (1)

𝑆𝑎𝑎 = 1𝑆𝑎 (1)1𝑠𝑏 (2) 1𝑆𝑎 (1)1𝑠𝑏 (2) = 𝑆𝑏𝑏 = 1

𝑆𝑎𝑏 (= 𝑆𝑏𝑎 ) = 1𝑆𝑎 (1)1𝑠𝑏 (2) 1𝑆𝑎 (2)1𝑠𝑏 (1) Overlap Integral (S)
1 1 1 1
𝐻𝑎𝑎 (= Hbb ) = 1𝑠𝑎 1 1𝑠𝑏 2 𝐻𝑎 1 + 𝐻𝑏 2 − 𝑟 − 𝑟 + 𝑟 + 𝑅 1𝑠𝑎 1 1𝑠𝑏 2
1𝑏 2𝑎 12 𝑎𝑏
1 1 1 1
= −1 + 1𝑠𝑎 1 1𝑠𝑏 2 − 𝑟 − 𝑟 − 𝑟 − 𝑅 1𝑠𝑎 1 1𝑠𝑏 2
1𝑏 2𝑎 12 𝑎𝑏
1 1 1 1
= −1 + 1𝑠𝑎 1 2
− − − +
𝑟1𝑏 𝑟2𝑎 𝑟12 𝑅𝑎𝑏
1𝑠𝑏 2 2 𝑑𝑟1 𝑑𝑟2 Coulomb Integral (J)
1 1 1
𝐻𝑎𝑏 = 𝐻𝑏𝑎 = 1𝑠𝑎 1 1𝑠𝑏 2 𝐻𝑎 1 + 𝐻𝑎 2 − 𝑟 − 𝑟 + 𝑟 1𝑠𝑎 2 1𝑠𝑏 1
1𝑏 2𝑎 12

1 1 1
= −𝑆 2 + 1𝑠𝑎 1 1𝑠𝑏 2 − 𝑟 − 𝑟 + 𝑟 1𝑠𝑎 2 1𝑠𝑏 1 Exchange Integral (K)
1𝑏 2𝑎 12
 H2 Molecule: Heitler – London Solutions

−1 + 𝐽 − 𝐸 −𝑆 2 + 𝐾 − 𝐸𝑆 2
Determinant =0
−𝑆 2 + 𝐾 − 𝐸𝑆 2 −1 + 𝐽 − 𝐸

Energies 𝐽𝐾
𝐸 = −1 +
1  𝑆2
Quantum mechanical Exchange K arising due to Pauli’
Antisymmetry is responsible for covalent Bonding
Heitler Quote:
Physics eats chemistry with a spoon.
Birth of (Heitler – London – Slater – Pauling)
Valence Bond Theory
Pauling referred electron Exchange as
‘Resonance’ between Structures.(1928)

1
Wave Functions  = 1𝑠𝑎 1 1𝑠𝑏 2  1𝑠𝑎 2 1𝑠𝑏 (1
2(1𝑆 2 )
 H2 Molecule: Molecular Orbital Model
Trial Wave Function  𝑇𝑟𝑖𝑎𝑙 = 1𝑠𝑎 1 + 1𝑠𝑏 1 ∗ (1𝑠𝑎 2 + 1𝑠𝑏 2 )
= σ𝑔 1 ∗ σ𝑔 2
1
Hamiltonian 𝐻= 𝐻2+ 1 + 𝐻2+ 2 +
𝑟12
σ𝑔 1 α(1) σ𝑔 1 β(1)
Secular Determinant σ𝑔 2 α(2) σ𝑔 2 β(2)

1
Energies 𝐸 = σ𝑔 1 ∗ σ𝑔 2 𝐻2+ 1 + 𝐻2+ 2 + 𝑟 σ𝑔 1 ∗ σ𝑔 2
12

1
𝐸 = 2𝐸𝐻+2 + σ𝑔 1 2
σ 2
𝑟12 𝑔
2
𝑑𝑟1 𝑑𝑟2 Coulomb Integral (J)

Delocalization of electrons from Atomic Orbitals to

Molecular Orbital (Bonding) Causes covalent Bonding
Birth of (Hund – Mulliken – Slater – Lennard-Jones ) Molecular Orbital Theory
 Excited H2 Molecule: Hund – Mullikan Model
1
Trial Wave Function  𝑇𝑟𝑖𝑎𝑙 = (σ𝑔 1 ∗ σ𝑢 2  σ𝑔 2 ∗ σ𝑢 1 )
2

1
Hamiltonian 𝐻= 𝐻2+ 1 + 𝐻2+ 2 +
𝑟12

1 1
Energies 𝐸1 = 𝐸σ𝑔 + 𝐸σ𝑢 + σ𝑔 1 ∗ σ𝑢 2 𝑟12
σ𝑔 1 ∗ σ𝑢 2 + σ𝑔 1 ∗ σ𝑢 2 𝑟12
σ𝑔 2 ∗ σ𝑔 1

1 1
𝐸 3 = 𝐸σ𝑔 + 𝐸σ𝑢 + σ𝑔 1 ∗ σ𝑢 2 𝑟 σ𝑔 1 ∗ σ𝑢 2 − σ𝑔 1 ∗ σ𝑢 2 𝑟 σ𝑔 2 ∗ σ𝑢 1
12 12

Coulomb Integral (J) Exchange Integral (K)

Both J and K are Positive (Repulsive), but J is larger in magnitude than K

Triplet State lies Lower in Energy than Singlet due to Reduced Repulsion
 Valence Bond Theory vs Molecular Orbital Theory
𝑴𝑶 = σ𝑔 1 ∗ σ𝑔 2 = 1𝑠𝑎 1 + 1𝑠𝑏 1 ∗ (1𝑠𝑎 2 + 1𝑠𝑏 2 ))

Trial Wave Function = 1𝑠𝑎 1 1𝑠𝑎 2 + 1𝑠𝑎 1 1𝑠𝑏 2 + 1𝑠𝑏 1 1𝑠𝑎 2 + 1𝑠𝑏 1 1𝑠𝑏 2

(H-…H+) 2(H.…H.) 𝑽𝑩 (H+…H-)

MOT overemphasizes ionic contributions VBT totally ignores it
2 1 2
Lim EMO = Lim 2𝐸𝐻2+ + σ𝑔 1 σ𝑔 2 𝑑𝑟1 𝑑𝑟2 = 2𝐸𝐻+ (Horrible)
𝑅𝑎𝑏 →∞ 𝑟12 →∞ 𝑟12 2

Dissociation 𝐽𝐾
Lim EVB = 𝑟12
Lim (2𝐸𝐻 + ) = 2𝐸𝐻 (Wonderful)
𝑅𝑎𝑏 →∞ →∞ 1  𝑆2
𝑟1𝑏 →∞
𝑟2𝑎 →∞

MOT: Including Excited States and Configuration Interaction Tractable

Improvement
VBT: Including ionic contributions Intractable due to exponential growth

MOT LCAO expansion allows cognition of atoms in molecules.

Clarity
VBT through hybridization allows cognition of atoms as well as bonds (Lewis 2c-2e).
 Configuration Interaction H2
The two molecular orbitals arrived for H2 molecule are + = 1𝑠𝑎 + 1𝑠𝑏 − = 1𝑠𝑎 − 1𝑠𝑏
The Possible spatial Configurations are bonding Anti-bonding
2 1 1 2 𝟏 = + (1) + (2) Sym
′𝟐 = + (1) − (2) unsym 𝟐 = + (1) − (2) + + (2) − (1)
′𝟑 = + (2) − (1) unsym 𝟑 = + (1) − (2) − + (2) − (1)
1 2 1 2
𝟒 = − (1) − (2) Sym
Interacting Configuration 𝟏 and 𝟐  = 𝑪𝟏 𝟏 + 𝑪𝟐 𝟐 𝐻11 − 𝐸𝑆11 𝐻12 − 𝐸𝑆12
=0
𝐻21 − 𝐸𝑆21 𝐻22 − 𝐸𝑆22
𝐻11 = 𝟏 𝐻 𝟏 = 𝐸+
𝑆11 = 𝟏 𝟏 =1
𝐻12 = 𝟏 𝐻 𝟐 = + (1) + (2) 𝐻 + (1) − (2) + + (2) − (1)
𝑆12 = 𝟏 𝟐 =0
= + (1) + (2) 𝐻 + (1) − (2) + + (1) + (2) 𝐻 + (2) − (1)
𝑆21 = 𝟐 𝟏 =0
= + (1) 𝐻 + (1) ∗ + (2) 𝐻 − (2) + + (1) 𝐻 − (1) ∗ + (2) 𝐻 + (2) 𝑆22 = 𝟐 𝟐 =1
=0 1𝑠𝑎 (2) + 1𝑠𝑏 (2) 𝐻 1𝑠𝑎 2 − 1𝑠𝑏 (2) = 0
Brillouin’s Theorem :
𝐻21 = 𝐻12 = 0 Interchanging nuclei changes the sign of the Configurations differing by
𝐻22 = 𝟐 𝐻 𝟐 = 𝐸− integral, but Hamiltonian is invariant. Singly Excitations will not mix.
 Configuration Interaction H2 Contd.
Interacting Configuration 𝟏 and 𝟒

𝟏 = + (1) + (2) + = 1𝑠𝑎 + 1𝑠𝑏 − = 1𝑠𝑎 − 1𝑠𝑏

1 2 𝟒 = − (1) − (2) Bonding Anti-bonding
 = 𝑪𝟏  𝟏 + 𝑪𝟒  𝟒 (Change of notation)
1 2  = 𝑪+  + + 𝑪−  − = 𝑪+ + (1) + (2) + 𝑪− − (1) − (2)

= 𝑪+ 1𝑠𝑎 (1) + 1𝑠𝑏 (1 ) ∗ 1𝑠𝑎 (2) + 1𝑠𝑏 (2 + 𝐶− ( 1𝑠𝑎 1 − 1𝑠𝑏 (1) ∗ 1𝑠𝑎 2 − 1𝑠𝑏 (2)

= 𝑪+ 1𝑠𝑎 (1)1𝑠𝑎 (2) + 1𝑠𝑎 1 1𝑠𝑏 2 + 1𝑠𝑏 1 1𝑠𝑎 2 + 1𝑠𝑏 1 1𝑠𝑏 2 +

𝑪− ( 1𝑠𝑎 (1)1𝑠𝑎 (2 − 1𝑠𝑎 1 1𝑠𝑏 2 − 1𝑠𝑏 1 1𝑠𝑎 2 + 1𝑠𝑏 1 1𝑠𝑏 2

= 1𝑠𝑎 1 1𝑠𝑏 2 + 1𝑠𝑏 1 1𝑠𝑎 2 𝑪+ − 𝑪− + (1𝑠𝑎 1 1𝑠𝑎 2 + 1𝑠𝑏 1 1𝑠𝑏 2 ) 𝑪+ + 𝑪−

𝑽𝑩 𝒊𝒐𝒏𝒊𝒄
MO Wave function with configuration interaction generates VB wavefunction with ionic structures
 Relationship Between MO and VB Trial Wavefunctions

Spin

Superposition Molecular Product MO Configuration

Orbitals Wavefunction Interaction
Atomic Accurate
Orbitals Results
Product Resonance Superposition VB Ionic
Structures Wavefunction Structures

Spin
 HF-SCF Theory with Molecular Orbitals
For a closed Shell system, the variational method leads to Fψi= Eiψi , F  Fock Operator
𝒏 𝑁 𝑛
1 2 𝑍μ
𝑭= 𝐹 𝑖 𝐹 𝑖 = − 𝛻𝑖 − + 2𝐽𝑗 − 𝐾𝑗
2 𝑟μ𝑖
𝒊=𝟏 μ=1 𝑗=𝑖 𝑛

For molecules, the one e-n wave-functions are represented by LCAO approximation. 𝞧𝑖 = 𝐶𝑖𝑗 χ𝑖
𝑗=1
The atomic orbitals are represented by a basis set using STOs or GTOs
The entries of the Slater determinant are represented by these one-electron spin MOs.
The resulting Hartree-Fock equations are referred to as Roothan’s equations.
Matrix Formulation leads to FC = SCE. 𝐹11 − 𝐸𝑆11 ⋯ 𝐹1𝑛 − 𝐸𝑆𝑁1
⋮ ⋱ ⋮ =0
𝐹1𝑁 − 𝐸𝑆1𝑁 ⋯ 𝐹𝑁𝑁 − 𝐸𝑆𝑁𝑁
𝑛𝑢𝑐𝑙𝑒𝑖
1 2 1 1
𝐹μν = μ − 𝛻𝑖 ν + 𝑧𝑘 μ− ν + 𝑃λσ μν λσ) − μλ νσ)
2 𝑟𝑘 2 𝑜𝑐𝑐𝑢𝑝𝑖𝑒𝑑
𝑘=1 λσ

μν λσ) = χμ (1)χν (1)

1
χμ 2 χν 2 𝑑𝑟1 𝑑𝑟2 Density Matrix 𝑃λσ = 2 𝐶λ𝑖 . 𝐶σ𝑖
𝑟12
𝑖
 HF-SCF Theory –Flow Chart
Compute Overlap Sij, one Compute the
Molecule Information Basis Set Trial Wave Function
and two e-n integrals Density Matrix P1

Construct and Solve

Molecular Geometry need to be
HF equations
chemically reasonable and should have
the right symmetry. Replace the initial Reconstruct the
Density Matrix Density Matix Pn
Basis Sets should be chosen based on
the available nature of the molecule No Intial Pn and Final Pn-1
time and Space resources. Density Matrix Similar?
YES
Trial Wave Functions should have right set of Output the MOs and
occupied MOs with the required symmetry and their Energies

significant HOMO-LUMO gap

Rest of them are similar to Atomic Hartree-Fock

 HOMO nuclear Diatomics

H2 Interaction Diagram He2 Interaction Diagram

E- E-

EH EH EHe EHe

E+ E+

The Qualitative one-electron picture of Bonding and Antibonding is retained

MO theory of Bonding starts with the construction of molecular orbitals

using Interaction Diagrams
 Avoided Crossing and sp Mixing

Mixing Criteria

Matching
Symmetry

Energetic
2p
Proximity

Comparable 2s
Orbital
Diffuseness
Without sp mixing With sp mixing

± ±
 Insufficient sp Mixing
Mixing Criteria

Matching
Symmetry

Energetic
Proximity 2p

Comparable
Orbital
3p
Diffuseness

3s

2s

Energy Mismatch Size Mismatch

Evolution of Energy Levels in sp Homonuclear Diatomics
Hetero-Nuclear Diatomics : An Example