Quantum Mechanics for Chemical Engineers Lecture 19

Molecular Orbital Theory

Byungchan Han
Department of Chemical & Biomolecular Engineering,Yonsei University
May 20, 2016 (Tuesday)
Heteronuclear Diatomic Molecule

HF

HF = cAψ H 1s + cBψ F 2p z
Ψ MO

Ψ anti−bond
MO,HF = c anti−bond
A
ψ H 1s + c anti−bond
B ψ F 2pz

Ψ bond
MO,HF = c bond
A
ψ H 1s + c B ψ F 2p z
bond

How to calculate these coefficients?

 The Variation Principle
• If an Arbitrary wavefunction (trial WF) is used to calculate the Energy,
the value calculated is Never Less than the True Energy (we never know it though)
• Basis of all modern molecular structure calculations.
• Systematic way of discussing Bond Polarity and finding the Coefficients in the LCAO

If we vary the coefficients in the Trial Wavefunction until the Lowest Energy is achieved
(by evaluating the Expectation Value of the Hamiltonian for each wavefunction),
then, those coefficients will be the Best (Optimum).

for H2+
e p̂ 2 e2 e2 e2
Ĥ = − − +
B 2m 4πε o r − R1 4πε o r − R2 4πε o R1 − R2
A
r ψ (r) = cAφ A (r) + cBφ B (r)
R2
R1
E = ψ Ĥ ψ min

∫ Ĥψ dτ
ψ *
∫ ( cAφA + cBφB ) Ĥ ( cAφA + cBφB ) dτ cA2 ∫ φ A Ĥ φ A dτ + cB2 ∫ φ B Ĥ φ B dτ + cA cB ∫ φ A Ĥ φ B dτ + cB cA ∫ φ B BĤ φ A dτ
E= = =
∫ ψ ψ dτ
*
(
∫ A B dτ
c A + c B ) 2
cA2 ∫ φ A2 dτ + cB2 ∫ φ B2 dτ + 2cA cB ∫ φ Aφ B dτ

cA2α A + cB2α B + 2cA cB β

E=
cA2 + cB2 + 2cA cB S
 The Variation Principle
for H2+ cA2α A + cB2α B + 2cA cB β
e E=
cA2 + cB2 + 2cA cB S
A B
⎧α A = φ A Ĥ φ A dτ ( ≠ Eo why? ) < 0 → Coulomb (Onsite) Integral
r
R2 ⎪ ∫
⎪α = φ Ĥ φ dτ < 0 → Coulomb (Onsite) Integral
R1 ⎪ B ∫ B B
⎨
⎪β = ∫ φ B Ĥ φ A dτ = ∫ φ A Ĥ φ B dτ → Resonance (Hopping) Integral
⎪
⎪⎩S = ∫ φ Bφ A dτ = ∫ φ Aφ B dτ → Overlap Integral

p̂ 2 e2 e2 e2
Ĥ = − − +
2m 4πε o r − R1 4πε o r − R2 4πε o R1 − R2

ψ (r) = cAφ A (r) + cBφ B (r)

⎛ p̂ 2 e2 e2 ⎞
α A = ∫ φ A Ĥ φ A dτ = ∫ φ A ⎜ − − ⎟⎠ φ A dτ
E = ψ Ĥ ψ min ⎝ 2m 4πε o r − R1 4πε o r − R2
e2
= ε o (= −13.6 eV ) − ∫ φ A φ A dτ = ε
4πε o r − R2

• = The energy of an electron sitting in the orbital of A atom in the presence of the other nuclei
• Onsite integrals include the contribution of the neighboring atoms
 The Variation Principle
for H2+ cA2α A + cB2α B + 2cA cB β
e E=
cA2 + cB2 + 2cA cB S
A B
⎧α A = φ A Ĥ φ A dτ ( ≠ Eo why? ) < 0 → Coulomb (Onsite) Integral
r
R2 ⎪ ∫
⎪α B = φ B Ĥ φ B dτ < 0 → Coulomb (Onsite) Integral
R1 ⎪ ∫
⎨
⎪β = ∫ φ B Ĥ φ A dτ = ∫ φ A Ĥ φ B dτ → Resonance (Hopping) Integral
⎪
⎪⎩S = ∫ φ Bφ A dτ = ∫ φ Aφ B dτ → Overlap Integral

p̂ 2 e2 e2 e2
Ĥ = − − +
2m 4πε o r − R1 4πε o r − R2 4πε o R1 − R2

ψ (r) = cAφ A (r) + cBφ B (r)

⎛ p̂ 2 e2 e2 ⎞
E = ψ Ĥ ψ β = ∫ φ B Ĥ φ A dτ = ∫ φ B ⎜ − − ⎟⎠ φ A dτ
min ⎝ 2m 4πε o r − R1 4πε o r − R2
e2
= ε o S12 − ∫ φ A φ A dτ
4πε o r − R2
• They couple the state ΦA to the state ΦB —> thus, allow the electron to hop from one atom to one of its
neighbors.
• It can also be interpreted as the hopping frequency, i.e. the frequency of the electron jumping from state
ΦA to the state ΦB.
 The Variation Principle
∂E ∂E
Ψ = cA A + cB B =0 = 0 → Secular Equation
∂cA ∂cB
⎧α A = φ A Ĥ φ A dτ ( ≠ Eo why? ) < 0 → Coulomb (Onsite) Integral
⎪ ∫
cA2α A + cB2α B + 2cA cB β ⎪α B = φ B Ĥ φ B dτ < 0 → Coulomb (Onsite) Integral
E= ⎪ ∫
cA2 + cB2 + 2cA cB S ⎨
⎪β = ∫ φ B Ĥ φ A dτ = ∫ φ A Ĥ φ B dτ → Resonance (Hopping) Integral
⎪
⎪⎩S = ∫ φ Bφ A dτ = ∫ φ Aφ B dτ → Overlap Integral

∂E
= 0 → (α A − E ) cA + ( β − ES ) cB = 0 ⎡ α A − E β − ES ⎤ ⎡ cA ⎤ ⎡ 0 ⎤
∂cA
⎢ ⎥⎢ ⎥=⎢ ⎥
∂E
= 0 → ( β − ES ) cA + (α B − E ) cB = 0 ⎢⎣ β − ES α B − E ⎥⎦ ⎢⎣ cB ⎥⎦ ⎣ 0 ⎦
∂cB

⎡ α A − E β − ES ⎤ α A + α B − 2 β S ± (α A + α B − 2 β S ) − 4(1− S 2 ) (α Aα B − β 2 )
2

det ⎢ ⎥ = 0 E± =
⎢⎣ β − ES α B − E ⎥⎦ 2(1− S 2 )

Two AO —> Two Coefficients —> 2 × 2 Matrix —> Two Energies —> Two Sets of Coefficients
 The Variation Principle
⎧α A = φ A Ĥ φ A dτ
Ψ = cA A + cB B
∂E
=0
∂E
= 0 → Secular Equation ⎪ ∫
∂cA ∂cB
⎪α B = φ B Ĥ φ B dτ < 0
⎪ ∫
⎨
⎪β = ∫ φ B Ĥ φ A dτ = ∫ φ A Ĥ φ B dτ
α A + α B − 2β S ± (α A + α B − 2β S )2 − 4(1− S 2 )(α Aα B − β 2 ) ⎪
E± = ⎪⎩S = ∫ φ Bφ A dτ = ∫ φ Aφ B dτ
2(1− S 2 )

For a Homonuclear Diatomic Molecule For a Heteronuclear Diatomic Molecule with S = 0

⎧ α +β
E =
⎪⎪ + 1+ S αA +αB 1 ⎛ 2β ⎞
2

αA = αB = α → ⎨ → E+ < E− E± = ± (α A − α B ) 1+ ⎜
⎝ α A − α B ⎟⎠
⎪ E− = α − β
2 2
⎪⎩ 1− S

• Ionization energies of H1s and F2pz electrons: 13.6 eV and 17.4 eV

—> αH ~ −13.6 eV and αF ~ −17.4 eV.
• For β = −1.0 eV & and S = 0 —> E+ = −17.6 eV and E− = −13.4 eV.
• For β = −1.0 eV & S = 0.2 —> E+ = −18.9 eV and E− = −13.0 eV.
• As S↑ Energy Split Increases
 Features of Solutions

Ψ = cA A + cB B
α A + α B − 2β S ± (α A + α B − 2β S )2 − 4(1− S 2 )(α Aα B − β 2 )
E± =
2(1− S 2 )

For a Heteronuclear Diatomic Molecule

2
α +αB 1 ⎛ 2β ⎞
E± = A ± (α A − α B ) 1+ ⎜
2 2 ⎝ α A − α B ⎟⎠

⎧ β2
⎪ E+ = α A + α − α
When α A − α B ≫ 2 β → ⎪ A B
⎨
⎪E = α − β 2

⎪⎩ − B
αA −αB

As |αA − αB|↑ the bonding and antibonding effects↓: when |αA − αB| is very large, the energies
of the resulting molecular orbitals differ only slightly from those of the atomic orbitals.
The strongest bonding and antibonding effects are obtained when the two contributing orbitals
have closely similar energies.
The difference in energy between core and valence orbitals is the justification for neglecting the
contribution of core orbitals to bonding. The core orbitals of one atom have a similar energy to
the core orbitals of the other atom; but core–core interaction is largely negligible because the
overlap between them (and hence the value of β) is so small.
 Coefficients
∂E ∂E ⎧⎪(α A − E ) cA + ( β − ES ) cB = 0
Ψ = cA A + cB B =0 = 0 → Secular Equation ⎨
∂cA ∂cB ⎪⎩( β − ES ) cA + (α B − E ) cB = 0

α A + α B − 2β S ± (α A + α B − 2β S ) − 4(1− S 2 )(α Aα B − β 2 )
2

E± =
2(1− S 2 )

⎧ αA − E 1
(α
⎪ A − E ) c + ( β − ES ) c =
β − ES
cA cA =
⎧⎪ ⎛ α − E ⎞ 2
A B
⎨ ⎛ αA − E ⎞
⎨ ⎜
1+ A
⎟ − 2S ⎜⎝ β − ES ⎟⎠
⎪ ψ *ψ dτ = c 2 + c 2 + 2c c S = 1
⎩∫ A B A B ⎪⎩ ⎝ β − ES ⎠

For a Homonuclear Diatomic Molecule For a Heteronuclear Diatomic Molecule with S = 0

⎧ α +β 1 ⎧ ⎧
=
1
E =
⎪ + 1+ S , c = = cB α + α 1 ⎛ 2 β ⎞
2
⎪ c
+ (α A − α B ) 1+ ⎜
A
⎪
A
2(1+ S) ⎪ E+ = A B
⎧⎪ ⎛ α − E ⎞ 2 ⎫⎪
⎝ α A − α B ⎟⎠ ⎪
αA = αB = α → ⎨ ⎪⎪ 2 2 ⎪ ⎨1+ ⎜
A
⎟⎠ ⎬
⎝ β
⎪ E− = α − β , c A = 1
= −cB
⎨ →⎨ ⎩⎪ ⎭⎪
⎪ ⎪
2
⎪⎩ αA +αB 1 ⎛ 2β ⎞
1− S 2(1− S) ⎪ E− = − (α A − α B ) 1+ ⎜ ⎪c = ⎛ α A − E ⎞ c
⎪⎩ 2 2 ⎝ α A − α B ⎟⎠ ⎪ B ⎜⎝ β ⎟⎠ A
⎩
 Molecular Energy Diagram of HF

HF

In H-F (using H1s and F2pz orbitals as a basis) we set αH = −13.6 eV and αF = −17.4 eV. Ψ + = 0.24ψ H1s + 0.97ψ F2pz
For β = −1.0 eV as a typical value and S = 0, E+ = −17.6 eV and E− = −13.4 eV. Ψ − = 0.97ψ H1s − 0.24ψ F2pz
 Polyatomic Molecules
ψ = ∑ ciφi General Form of LCAO
i

The sum extend over All the Valence orbitals of All the Atoms in the molecule
Derive Secular Equations —> Secular Determinant —> Energy —> Coefficients

Unlike Diatomic molecules the Polyatomic molecules have greater ranges of shapes:
• Linear, Planar, Angular structures
Bond Angles and Bond Lengths are determined by Ground State Energy

Conjugated system
• System of connected p-orbitals with delocalized
electrons in molecules with alternating single and
multiple bonds
• It in general, it lowers the overall energy of the
molecule and increase stability.
• Lone pairs, radicals or carbenium ions may be
part of the system. Amphotericin B is an example of a yellow-colored
• The compound may be cyclic, acyclic, linear or
polyene antifungal (antimycotic) agent. Note the
mixed. alternating double and single bonds in the center
 The Hückel Approximation

The π MO Energy Level Diagrams of Conjugated Molecules can be constructed using a set of
approximations suggested by Erich Hückel in 1931.
The π orbitals are treated separately from the σ orbitals
σ orbitals: form a rigid framework that determines the general shape of the molecule.
π orbitals: additional stability?
For example: all the C atoms are treated identically, so all the Coulomb integrals α for the
atomic orbitals that contribute to the π orbitals are set equal.
In ethene, we take the σ bonds as fixed, and concentrate on finding the energies of the
single π bond and its companion antibond.

∂E ∂E
ψ (r) = cAφ A (r) + cBφ B (r) =0 = 0 → Secular Equation αA = αB = α
∂cA ∂cB

∂E ⎧α A = φ A Ĥ φ A dτ
∂cA
= 0 → (α − E ) cA + ( β − ES ) cB = 0
⎪ ∫
⎪α B = φ B Ĥ φ B dτ < 0
∂E
= 0 → ( β − ES ) cA + (α − E ) cB = 0 ⎪ ∫
∂cB ⎨
⎪β = ∫ φ B Ĥ φ A dτ = ∫ φ A Ĥ φ B dτ
⎡ α − E β − ES ⎤ ⎡ cA ⎤ ⎡ 0 ⎤ ⎪
⎢ ⎥⎢ ⎥=⎢ ⎥ ⎪⎩S = ∫ φ Bφ A dτ = ∫ φ Aφ B dτ
⎢⎣ β − ES α − E ⎥⎦ ⎢⎣ cB ⎥⎦ ⎣ 0 ⎦

In principle, all the resonance integrals and overlap integrals should be included
 The Hückel Approximation
∂E ∂E
ψ (r) = cAφ A (r) + cBφ B (r) =0 = 0 → Secular Equation αA = αB = α
∂cA ∂cB

∂E ⎧α A = φ A Ĥ φ A dτ
∂cA
= 0 → (α − E ) cA + ( β − ES ) cB = 0
⎪ ∫
⎪α B = φ B Ĥ φ B dτ < 0
∂E
∂cB
= 0 → ( β − ES ) cA + (α − E ) cB = 0 ⎪ ∫
⎨
⎪β = ∫ φ B Ĥ φ A dτ = ∫ φ A Ĥ φ B dτ
⎡ α − E β − ES ⎤ ⎡ cA ⎤ ⎡ 0 ⎤ ⎪
⎢ ⎥⎢ ⎥=⎢ ⎥ ⎪⎩S = ∫ φ Bφ A dτ = ∫ φ Aφ B dτ
⎢⎣ β − ES α − E ⎥⎦ ⎢⎣ cB ⎥⎦ ⎣ 0 ⎦

All overlap integrals are set equal to zero.

All resonance integrals between non-neighbors are set equal to zero.
All remaining resonance integrals are set equal (to β ).

All diagonal elements = α − E.

Off-diagonal elements btw neighboring atoms = β.
All other elements = 0.

⎛⎡ α −E β ⎤⎞ ⎧ E+ = α + β (Bonding Orbital)
det ⎜ ⎢ ⎥⎟ = 0 → ⎨
⎜⎝ ⎢ β
⎣
α −E ⎥⎦⎟⎠ ⎩ E− = α − β (Antibonding Orbital) The Hückel molecular orbital energy level
diagram for the π orbitals of ethene.
 The Hückel Approximation
⎛⎡ α −E β ⎤⎞ ⎧ E+ = α + β (Bonding Orbital)
det ⎜ ⎢ ⎥⎟ = 0 → ⎨
⎜⎝ ⎢ β
⎣
α −E ⎥⎦⎟⎠ ⎩ E− = α − β (Antibonding Orbital)

LUMO (Lowest Unoccupied Molecular Orbital)

Frontier Orbitals: HOMO, LUMO

HOMO (Highest Occupied Molecular Orbital)

• The Frontier Orbitals are important because they are largely responsible for many of the chemical
and spectroscopic properties of the molecule.
• For example, we can estimate that 2|β|is the π * ← π excitation energy of ethene, the energy
required to excite an electron from the 1π to the 2π orbital.
• The constant β is often left as an adjustable parameter; an approximate value for π bonds formed
from overlap of two C2p atomic orbitals is about − 2.4 eV (− 230 kJ mol−1).
 The Matrix Formulation of the Hückel Method
∂E ∂E
ψ (r) = cAφ A (r) + cBφ B (r) =0 = 0 → Secular Equation αA = αB = α
∂cA ∂cB

∂E ⎧α A = φ A Ĥ φ A dτ
∂cA
= 0 → (α − E ) cA + ( β − ES ) cB = 0
⎪ ∫
⎪α B = φ B Ĥ φ B dτ < 0
∂E
∂cB
= 0 → ( β − ES ) cA + (α − E ) cB = 0 ⎪ ∫
⎨
⎪β = ∫ φ B Ĥ φ A dτ = ∫ φ A Ĥ φ B dτ
⎡ α − E β − ES ⎤ ⎡ cA ⎤ ⎡ 0 ⎤ ⎪
⎢ ⎥⎢ ⎥=⎢ ⎥ ⎪⎩S = ∫ φ Bφ A dτ = ∫ φ Aφ B dτ
⎢⎣ β − ES α − E ⎥⎦ ⎢⎣ cB ⎥⎦ ⎣ 0 ⎦

( H AA − ESAA ) cA + ( H AB − ESAB ) cB = 0 ( H AA − Ei SAA ) ci,A + ( H AB − Ei SAB ) ci,B = 0

( H BA − ESBA ) cA + ( H BB − ESBB ) cB = 0 ( H BA − Ei SBA ) ci,A + ( H BB − Ei SBB ) ci,B = 0

⎛⎡ H SAB ⎤⎞ ⎡ ci,A ⎤
H AB ⎤
( )
⎡ SAA
=⎜⎢
AA

⎜⎝ ⎢ H BA
⎥ − Ei ⎢ ⎥⎟ ⎢ ⎥=0 = H! − Ei S! c!i = 0 → Hc
! = S!c! E
H BB ⎥ ⎢⎣ SBA SBB ⎥⎟⎠ ⎢ ci,B ⎥⎦ i i i
⎣ ⎦ ⎦ ⎣

⎡ c1,A c2,A ⎤ ⎡ E1 0 ⎤ ⎡ H AA − Ei SAA H AB − Ei SAB ⎤ ⎡ ci,A ⎤

c! = ⎢ ⎥ E=⎢ ⎥ ⎢ ⎥⎢ ⎥=0
⎢⎣ c1,B c2,B ⎥⎦ ⎢⎣ 0 E2 ⎥
⎦ ⎢⎣ H BA − Ei SBA H BB − Ei SBB ⎥ ⎢ ci,B
⎦⎣ ⎥⎦

→ H! c! = S!c!E!
 The Matrix Formulation of the Hückel Method
∂E ∂E
ψ (r) = cAφ A (r) + cBφ B (r) =0 = 0 → Secular Equation αA = αB = α
∂cA ∂cB

∂E
= 0 → (α − E ) cA + ( β − ES ) cB = 0 ⎧α A = φ A Ĥ φ A dτ
∂cA ⎪ ∫
⎪α = φ Ĥ φ dτ < 0
⎪ B ∫ B B
∂E
∂cB
= 0 → ( β − ES ) cA + (α − E ) cB = 0
⎨
⎡ H AA − Ei SAA H AB − Ei SAB ⎤ ⎡ ci,A ⎤
⎪β = ∫ φ B Ĥ φ A dτ = ∫ φ A Ĥ φ B dτ ⎢ ⎥⎢ ⎥=0
⎡ α − E β − ES ⎤ ⎡ cA ⎤ ⎡ 0 ⎤ ⎪ ⎢⎣ H BA − Ei SBA H BB − Ei SBB ⎥ ⎢ ci,B
⎦⎣ ⎥⎦
⎢ ⎥⎢ ⎥=⎢ ⎥ ⎪⎩S = ∫ φ Bφ A dτ = ∫ φ Aφ B dτ
⎢⎣ β − ES α − E ⎥⎦ ⎢⎣ cB ⎥⎦ ⎣ 0 ⎦

⎛⎡ H H AB ⎤ ⎡ SAA SAB ⎤⎞ ⎡ ci,A ⎤

=⎜⎢
AA

⎜⎝ ⎢ H BA
⎥ − Ei ⎢
H BB ⎥
⎥⎟ ⎢
SBB ⎥⎟⎠ ⎢ ci,B ⎥⎦
( )
⎥ = H! − Ei S! c!i = 0 → Hc
! = S!c! E
i i i
⎣ ⎦ ⎢⎣ SBA ⎦ ⎣

⎡ c1,A c2,A ⎤ ⎡ E1 0 ⎤
c! = ⎢ ⎥ E=⎢ ⎥ → H! c! = S!c!E! = c!E!
⎢⎣ c1,B c2,B ⎥
⎦ ⎢⎣ 0 E2 ⎥
⎦
Matrix Diagonalization
In the Hückel Approximation,

⎛⎡ H =α
=⎜⎢
AA H AB = β ⎤ ⎡ SAA = 1 SAB = 0
⎥ − Ei ⎢
⎤⎞ ⎡ ci,A
⎥⎟ ⎢
⎤
⎥ = 0 → H! c! = cE
! c! −1H! c! = E!
⎜⎝ ⎢ H BA = β H BB = α ⎥ ⎢⎣ SBA = 0 SBB = 1 ⎥⎦⎟⎠ ⎢⎣ ci,B ⎥⎦
⎣ ⎦

One you diagonalize the Hamiltonian Matrix you can find the Energy (Eigenvalues) and then the coefficients
 Example: Butadiene
Setup and sole the matrix equations within the HÜckel approximation for the π orbitals of Butadiene.

⎧α A = φ A Ĥ φ A dτ
⎡ H 11 H 12 H 13 H 14 ⎤ ⎪ ∫
⎢ ⎥
⎪α B = φ B Ĥ φ B dτ < 0
! ⎢
H=⎢
H 21 H 22 H 23 H 24 ⎥ ⎪ ∫
H 31 H 32 H 33 H 34 ⎥ ⎨
⎢ ⎥ ⎪β = ∫ φ B Ĥ φ A dτ = ∫ φ A Ĥ φ B dτ
⎢⎣ H 41 H 42 H 43 H 44 ⎥⎦ ⎪
⎪⎩S = ∫ φ Bφ A dτ = ∫ φ Aφ B dτ
In the Hückel Approximation,
⎡ α β 0 0 ⎤ ⎡ 0 1 0 0 ⎤
⎢ ⎥ ⎢ ⎥
All S = 0
! =⎢
β α β 0 ⎥ 1 0 1 0
H = α 1! + β ⎢ ⎥
All β between non-neighbors are = 0 ⎢ 0 β α β ⎥ ⎢ 0 1 0 1 ⎥
All remaining resonance integrals are set equal (to β ). ⎢ ⎥ ⎢⎣ 0 0 1 0 ⎥⎦
⎢⎣ 0 0 β α ⎥
⎦
By software in general
⎡ ⎤
⎡ 1.62 0 0 0 ⎤ ⎢ α + 1.62 β 0 0 0
⎥
⎢ ⎥
=E
α + 0.62
⎥=⎢
0 0.62 0 0 0 0 0 ⎥
= α 1! + β ⎢
⎢ 0 0 −0.62 0 ⎥ ⎢ 0 0 α − 0.62 β 0 ⎥
⎢⎣ 0 0 0 −0.62 ⎥⎦ ⎢⎢ 0 0 0 α − 0.62 β
⎥
⎥⎦
⎣

! c = E!
c! −1H!
 1 2 3 4

1 α β 0 0
2 β α β 0
3 0 β α β
4
0 0 β α

1 2 3 4
 Example: Butadiene
Setup and sole the matrix equations within the HÜckel approximation for the π orbitals of Butadiene.

By software in general

⎡ 1.62 0 0 0 ⎤ ⎡ α + 1.62 β 0 0 0 ⎤
⎥ ⎢ ⎥
⎢
= α 1! + β ⎢
⎢ 0
0 0.62
0
0
−0.62
0
0
⎥=⎢
⎥ ⎢
0
0
α + 0.62
0
0
α − 0.62 β
0
0
⎥
⎥
=E
⎢⎣ 0 0 0 −0.62 ⎥⎦ ⎢⎢ 0 0 0 α − 0.62 β
⎥
⎥⎦
⎣

⎡ 0.372 0.602 0.602 −0.372 ⎤

⎢ ⎥
0.602 0.372 −0.372 0.602 ⎥
c! = ⎢
⎢ 0.602 −0.372 −0.372 −0.602 ⎥
⎢⎣ 0.372 −0.602 0.602 −0.372 ⎥⎦
c! −1H! c! = E!

E4 = α − 0.62 β , ψ 1 = −0.372φ A + 0.602φ B − 0.602φC + 0.372φ D ⎡ α β 0 0 ⎤

⎢ ⎥
E3 = α − 0.62 β , ψ 1 = +0.602φ A − 0.372φ B − 0.372φC + 0.602φ D β α β 0 ⎥
H! = ⎢⎢
E2 = α + 0.62 β , ψ 1 = +0.602φ A + 0.372φ B − 0.372φC − 0.602φ D 0 β α β ⎥
⎢ ⎥
E1 = α + 1.62 β , ψ 1 = +0.372φ A + 0.602φ B + 0.602φC + 0.372φ D ⎢⎣ 0 0 β α ⎥
⎦
 Example: Butadiene
Setup and sole the matrix equations within the HÜckel approximation for the π orbitals of Butadiene.

By software in general

⎡ 1.62 0 0 0 ⎤ ⎡ α + 1.62 β 0 0 0 ⎤
⎥ ⎢ ⎥
⎢
= α 1! + β ⎢
⎢ 0
0 0.62
0
0
−0.62
0
0
⎥=⎢
⎥ ⎢
0
0
α + 0.62
0
0
α − 0.62 β
0
0
⎥
⎥
=E
⎢⎣ 0 0 0 −0.62 ⎥⎦ ⎢⎢ 0 0 0 α − 0.62 β
⎥
⎥⎦
⎣

⎡ 0.372 0.602 0.602 −0.372 ⎤

⎢ ⎥
0.602 0.372 −0.372 0.602 ⎥
c! = ⎢
⎢ 0.602 −0.372 −0.372 −0.602 ⎥
⎢⎣ 0.372 −0.602 0.602 −0.372 ⎥⎦
c! −1H! c! = E!

E4 = α − 0.62 β , ψ 1 = −0.372φ A + 0.602φ B − 0.602φC + 0.372φ D ⎡ α β 0 0 ⎤

⎢ ⎥
E3 = α − 0.62 β , ψ 1 = +0.602φ A − 0.372φ B − 0.372φC + 0.602φ D β α β 0 ⎥
H! = ⎢⎢
E2 = α + 0.62 β , ψ 1 = +0.602φ A + 0.372φ B − 0.372φC − 0.602φ D 0 β α β ⎥
⎢ ⎥
E1 = α + 1.62 β , ψ 1 = +0.372φ A + 0.602φ B + 0.602φC + 0.372φ D ⎢⎣ 0 0 β α ⎥
⎦
 Example: Butadiene
E4 = α − 0.62 β , ψ 1 = −0.372φ A + 0.602φ B − 0.602φC + 0.372φ D
E3 = α − 0.62 β , ψ 1 = +0.602φ A − 0.372φ B − 0.372φC + 0.602φ D
E2 = α + 0.62 β , ψ 1 = +0.602φ A + 0.372φ B − 0.372φC − 0.602φ D
E1 = α + 1.62 β , ψ 1 = +0.372φ A + 0.602φ B + 0.602φC + 0.372φ D

• The greater the number of internuclear nodes the higher Orbital E

• Four electrons are accommodated: Ground-State configuration = 1π22π2.
LUMO
• Frontier orbitals: the 2π orbital (the HOMO, largely bonding) and
the 3π orbital (the LUMO, largely antibonding) .
• ‘Largely’ bonding means that an orbital has both bonding and antibonding HOMO
interactions between various neighbors, but the bonding effects dominate.
‘Largely antibonding’ indicates that the antibonding effects dominate.
π-electron binding energy for the Butadiene:

Eπ = 2 (α + 1.62 β ) + 2 (α + 0.62 β ) = 4α + 4.48 β

π-electron binding energy for the Ethene(Ethylene)

Eπ = 2 (α + β ) = 2α + 2 β

E of a Butadiene molecule lies lower by 0.48β (~ 110 kJ/mol) than the sum of two individual π bonds.
Delocalization Energy: Extra stabilization of a conjugated system compared with a set of localized π bonds

π-bond formation energy Eπ −bf = Eπ − N Cα = 4.48 β (Nc : # of Carbon atoms)

 Example: Cyclo-Butadiene

⎡ α β 0 β ⎤ ⎡ 0 1 0 1 ⎤ ⎡ 2 0 0 0 ⎤
⎢ ⎥ ⎢ ⎥ ⎢ ⎥
β α β 0 ⎥ 1 0 1 0 0 0 0 0 ⎥
H! = ⎢⎢ = α 1! + β ⎢ ⎥ diagonalization
""""""""""""""""# α 1! + ⎢
0 β α β ⎥ ⎢ 0 1 0 1 ⎥ ⎢ 0 0 0 0 ⎥
⎢ ⎥ ⎢⎣ ⎥⎦ ⎢⎣
⎢⎣ β 0 β α ⎥⎦ 1 0 1 0 0 0 0 −2 ⎥⎦

Eπ = α + 2 β , α , α , α − 2 β

Four electrons must be accommodated.

• 2 into the energy level of α + 2β
• 2 into energy levels of α.
• So, the total energy is therefore 4α + 4β.
Two isolated π bonds would have an energy 4α+4β, therefore, the delocalization energy is zero
 1 2 3 4

1 α β 0 β
2 β α β 0
3 0 β α β
4
β 0 β α
1

4
2

3
Example: Benzene and Aromatic Stability

1 2 3 4 5 6 6 electrons 2 4
a2u e1g

1 ⎡ α β 0 0 0 β ⎤
⎢ ⎥
2 ⎢ β α β 0 0 0 ⎥
Eπ = α ± 2 β , α ± β , α ± β
3 ⎢ 0 β α β 0 0 ⎥
⎢ ⎥ π-electron binding energy Eπ = 2 β = −460 kJ / mol
4 ⎢ 0 0 β α β 0 ⎥
⎢ Eπ = 2 (α + 2 β ) + 4 (α + 2 β ) = 6α + 8 β
5 0 0 0 β α β ⎥
⎢ ⎥ 3 × Eπisol = 3( 2α + 2 β )
6 ⎢⎣ β 0 0 0 β α ⎥⎦
π-bond formation energy 8 β
Example: Benzene and Aromatic Stability
Aromatic stability can be traced to two main contributions.
First, the shape of the regular hexagon is ideal for the formation of strong σ bonds: the σ
framework is relaxed and without strain: Valence Bond Theory
Second, the π orbitals are such as to be able to accommodate all the electrons in bonding
orbitals, and the delocalization energy is large: Molecular Orbital Theory

⎡ α β 0 β ⎤ ⎡ 0 1 0 1 ⎤ ⎡ 2 0 0 0 ⎤
⎢ ⎥ ⎢ ⎥ ⎢ ⎥
β α β 0 ⎥
H! = ⎢⎢
1 0 1 0 0 0 0 0 ⎥
C4H4 ⎥ = α 1! + β ⎢ ⎥ diagonalization
""""""""""""""""# α 1! + ⎢
0 β α β ⎢ 0 1 0 1 ⎥ ⎢ 0 0 0 0 ⎥
⎢ ⎥
⎢⎣ β 0 β α ⎥⎦ ⎢⎣ 1 0 1 0 ⎥⎦ ⎢⎣ 0 0 0 −2 ⎥⎦

E = α + 2β , α , α , α − 2β

Total π bonding energy = Eπ = 2(α + 2 β ) + 2α Delocalization Energy = 0

So, Planar Structure

(C4H4)2+ Total π bonding energy = Eπ = 2(α + 2 β ) Delocalization Energy = 2β < 0

So, Aromatic Structure