Quantum Mechanics for Chemical Engineers Lecture 18

Molecular Orbital Theory

Byungchan Han
Department of Chemical & Biomolecular Engineering,Yonsei University
May 17, 2016 (Tuesday)
 Where Are we?

LCAO Ψ, Coefficient

Variational Principles Coefficient, Energy

Molecular Energy Diagram Energy Levels, Band

 Heteronuclear Diatomic Molecules
Most Molecules are heteronuclear.
Bonding MO of heteronuclear diatomic molecule is composed of mostly the AO of
the more electronegative atom.

H2

The electron distribution in a covalent bond in a heteronuclear diatomic molecule is

not shared equally by the atoms because it is energetically favorable for the electron
pair to be found closer to one atom than the other —> Polar Bond
Partial negative (positive) charge on F(H)
 MO Formulation
Polar bond consisting of 2 electrons in a bonding MO.
Ψ = cA A + cB B cA ≠ cB, (if cA = cB it is homonuclear diatomic molecule)
⎧⎪ cA 2 : the proportion of the atomic orbital A in the bond
⎨ 2
⎪⎩ cB : the proportion of the atomic orbital B in the bond
HF
⎧⎪ cA 2 = cB 2 : Non-polar bond
⎨
⎪⎩cA = 0 & cB = 1 : H F ( pure ionic bond)
+ -

δ+ Electron pair closer to F atom

δ−

AO with the lower energy makes the larger contribution to the bonding MO.
AO with the higher energy makes the larger contribution to the anti-bonding MO.

Bonding σ orbital in HF is mainly F:2pz and the antibonding σ mainly H:1s in character.
Two electrons in the bonding orbital are most likely to be found in the F:2pz orbital,
Partial negative charge on the F and a partial positive charge on the H.
 MO Formulation: Energy and Composition
What values of energy must be used for the AO?
Typically it involves with many electron atoms (like F) and the exact energy
Ψ = cA A + cB B is known only after complicate calculations…
Can we estimate the energy from Ionization energy and electron affinity
information?

0 X+ + e- When completely lose electron

I(X) −I(X) − Eea (X)

Probably the energy of the AO?
2
-I(X) X When share electron with partner
Eea(X)
-I(X) - Eea(X) X- When completely gain electron
 MO Formulation: Energy and Composition

HF
−I(X) − Eea (X)
2

I(X) + Eea (X)

I (eV) Eea −
2
H 13.6 0.75 7.2
F 17.4 3.34 10.4

Ψ MO
HF = cAψ H 1s + cBψ F 2 pz

LCAO with these values of the energy

The atom with more negative energy value contribute the greater amount to the bonding orbital.
 Electronegativity (𝛘)
Measure of the power of an atom to attract electrons to itself when it is part of a compound
Pauling Electronegativity (𝛘P), (1932)
• D0(AA): the dissociation energies of A–A bonds
1/2
⎧⎪ D0 (AA) + D0 (BB) ⎫⎪ • D0(BB): the dissociation energies of B–B bonds
χ A − χ B = ⎨ D0 (AB) − ⎬ • D0(AB): the dissociation energy of an A–B bonds
⎪⎩ 2 ⎪⎭
• All in eV
Dimensionless

• Difference of the electronegativities

• Hydrogen was chosen as the reference (2.20), as it forms
covalent bonds with a large variety of elements
• ex) Do(H-H) = 4.52, Do(Cl-Cl) = 2.51, Do(H-Cl) = 4.47
χ P (H ) − χ P (Cl) = 1.0

• The greater the difference in EN the greater the Polar character of the bond.
• For HF = 1.78, For C– H bond = 0.35 (commonly regarded as almost nonpolar)
Electronegativity by Pauling Scale
Mulliken electronegativity scale: the higher electronegative the higher ionization energy and
the higher a higher electron affinity.

χM =
( I + Eea )
→χ = 1.35 χ M − 1.37
P
2

Correlation between the electronegativities by Mulliken (x-axis, in kJ/mol) and Pauling (y-axis).
Chicago 1929

Robert Mulliken
• Nobel prize in Chemistry (1966)
• 1917, B.S. Degree in Chemistry (MIT)
• 1921 Ph.D. Univ. Chicago (separation of
isotopes of mercury by evaporation)
 The Variation Principle
• If an arbitrary wavefunction is used to calculate the energy, the value calculated is never
less than the true energy: the basis of all modern molecular structure calculations.
• A 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).

∂E ∂E
Ψ = cA A + cB B ∂cA
=0
∂cB
= 0 → Secular Equation

∫ Ĥψ dτ
ψ *
∫ ( c A + c B ) Ĥ ( c A + c B ) dτ
A B A B ⎧α A = AĤA dτ ( ≠ Eo why? ) < 0 → Coulomb Integral
∫
E= = ⎪
∫ ψ ψ dτ ∫ ( c A + c B ) dτ
* 2
⎪α B = BĤB dτ < 0 → Coulomb Integral
A B
⎪ ∫
c ∫ AĤA dτ + c ∫ BĤB dτ +c c ∫ AĤB dτ + c c ∫ BĤA dτ
2 2 ⎨
=
A B A B B A
⎪β = ∫ BĤA dτ = ∫ AĤB dτ → Resonance (Hopping) Integral
c ∫ A dτ + c ∫ B dτ + 2c c ∫ AB dτ
2 2 2 2
⎪
⎪⎩S = ∫ BA dτ = ∫ AB dτ → Overlap Integral
A B A B

cA2α A + cB2α B + 2cA cB β

=
cA2 + cB2 + 2cA cB S
 The Variation Principle
∂E ∂E
Ψ = cA A + cB B =0 = 0 → Secular Equation
∂cA ∂cB
⎧α A = AĤA dτ ( ≠ Eo why?∵S ≠ 0 ) → Coulomb Integral
c α A + c α B + 2cA cB β
2 2
⎪ ∫
E= A B
⎪α B = BĤB dτ → Coulomb Integral
cA2 + c + 2cA cB S
2
B ⎪ ∫
⎨
⎪β = ∫ BĤA dτ = ∫ AĤB dτ → Resonance (Hopping) Integral
⎪
⎪⎩S = ∫ BA dτ = ∫ AB 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 − 2β S ± (α A + α B − 2β S )2 − 4(1− S 2 )(α Aα B − β 2 )
det ⎢ ⎥=0 E± =
⎢⎣ β − ES α B − E ⎥⎦ 2(1− S 2 )
 The Variation Principle
∂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 )2 − 4(1− S 2 )(α Aα B − β 2 )
E± =
2(1− S 2 )

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

⎧ α +β α +αB 1 ⎛ 2β ⎞
2

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

Ionization energies of H1s and F2p 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.
 Features of Solutions

Ψ = cA A + cB B 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 )

For a Heteronuclear Diatomic Molecule

2
αA +αB 1 ⎛ 2β ⎞
E± = ± (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

The the energy difference |αA − αB| between the interacting atomic orbitals increases the bonding
and antibonding effects decrease.
When the energy difference 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
(α
⎪ A − E ) c A + ( β − ES ) c B =
β − ES
cA cA =
1
⎨ ⎧⎪ ⎛ α − E ⎞ 2 ⎛ αA − E ⎞
⎪ ψ *ψ dτ = c 2 + c 2 + 2c c S = 1 −
⎩∫
⎨1+ ⎜
A
⎟ 2S ⎜⎝ β − ES ⎟⎠
⎪⎩ ⎝ β − ES ⎠
A B A B

For a Heteronuclear Diatomic Molecule with S = 0

For a Homonuclear Diatomic Molecule
⎧ ⎧ 1
⎧ α +β 1 α + α 1 ⎛ 2 β ⎞
2
c
⎪ A =
E =
⎪ + 1+ S , c = = cB ⎪ E+ = A B
+ (α A − α B ) 1+ ⎜ ⎪ ⎧⎪ ⎛ α − E ⎞ 2 ⎫⎪
⎝ α A − α B ⎟⎠
A
⎪ 2(1+ S) ⎪⎪ 2 2 ⎪ ⎨1+ ⎜
A
⎟⎠ ⎬
αA = αB = α → ⎨ ⎨ →⎨ ⎩⎪ ⎝ β ⎭⎪
⎪ E− = α − β , c A = 1
= −cB ⎪ αA +αB 1 ⎛ 2β ⎞
2
⎪
⎪⎩ ⎪ E− = − (α A − α B ) 1+ ⎜ ⎪c = ⎛ α A − E ⎞ c
⎝ α A − α B ⎟⎠
1− S 2(1− S)
⎪⎩ 2 2 ⎪ B ⎜⎝ β ⎟⎠ A
⎩

In H-F (using H1s and F2pz orbitals as a basis) we set αH = −13.6 eV and αF = −17.4 eV. Ψ + = 0.28ψ H + 0.96ψ F
For β = −1.0 eV as a typical value and S = 0, E+ = −17.6 eV and E− = −13.4 eV. Ψ − = 0.96ψ H − 0.28ψ F
 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 Ψ + = 0.24ψ H + 0.97ψ F
(α
⎪ A − E ) c + ( β − ES ) c =
β −
cA cA =
⎧⎪ ⎛ α − E ⎞ 2
A B
⎨ ES ⎛ αA − E ⎞ Ψ − = 0.97ψ H − 0.24ψ F
⎪ ψ *ψ dτ = c 2 + c 2 + 2c c S = 1 ⎨ ⎜
1+ A
⎟⎠ − 2S ⎜⎝ β − ES ⎟⎠
⎩∫ A B A B ⎩⎪ ⎝ β − ES
HF
For a Heteronuclear Diatomic Molecule with S = 0

⎧ ⎧ 1
α + α 1 ⎛ 2 β ⎞
2
c
⎪ A =
⎪ E+ = A + (α A − α B ) 1+ ⎜ ⎧ ⎫⎪
2
⎛ α − ⎞
B
⎪ ⎪
⎝ α A − α B ⎟⎠
E
⎪⎪ 2 2 ⎪ ⎨1+ ⎜
A
⎟⎠ ⎬
⎨ →⎨ ⎪⎩ ⎝ β ⎪⎭
⎪ ⎪
2
αA +αB 1 ⎛ 2β ⎞
⎪ E− = − (α A − α B ) 1+ ⎜ ⎪c = ⎛ α A − E ⎞ c
⎪⎩ 2 2 ⎝ α A − α B ⎟⎠ ⎪ B ⎜⎝ β ⎟⎠ A
⎩

In H-F (using H1s and F2pz orbitals as a basis) we set αH = −13.6 eV and αF = −17.4 eV.
For β = −1.0 eV as a typical value and S = 0, E+ = −17.6 eV and E− = −13.4 eV.
 Polyatomic Molecules

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

The π molecular orbital 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, and the latter form a rigid framework
that determines the general shape of the molecule.
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.
For example, 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 = cA A + cB B ∂cA
=0
∂cB
= 0 → Secular Equation αA = αB = α

⎧α A = AĤA dτ ( ≠ Eo why?∵S ≠ 0 ) → Coulomb Integral

∂E
= 0 → (α − E ) cA + ( β − ES ) cB = 0 ⎪ ∫
∂cA ⎪α B = BĤB dτ → Coulomb Integral
∂E ⎪ ∫
= 0 → ( β − ES ) cA + (α − E ) cB = 0 ⎨
∂cB ⎪β = ∫ BĤA dτ = ∫ AĤB dτ → Resonance (Hopping) Integral
⎪
⎡ α − E β − ES ⎤ ⎡ cA ⎤ ⎡ 0 ⎤ ⎪⎩S = ∫ BA dτ = ∫ AB dτ → Overlap Integral
⎢ ⎥⎢ ⎥=⎢ ⎥
⎢⎣ β − ES α − E ⎥⎦ ⎢⎣ cB ⎥⎦ ⎣ 0 ⎦

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

⎧α A = AĤA dτ ( ≠ Eo why?∵S ≠ 0 ) → Coulomb Integral

∂E
= 0 → (α − E ) cA + ( β − ES ) cB = 0 ⎪ ∫
∂cA ⎪α B = BĤB dτ → Coulomb Integral
∂E ⎪ ∫
= 0 → ( β − ES ) cA + (α − E ) cB = 0 ⎨
∂cB ⎪β = ∫ BĤA dτ = ∫ AĤB dτ → Resonance (Hopping) Integral
⎪
⎡ α − E β − ES ⎤ ⎡ cA ⎤ ⎡ 0 ⎤ ⎪⎩S = ∫ BA dτ = ∫ AB dτ → Overlap Integral
⎢ ⎥⎢ ⎥=⎢ ⎥
⎢⎣ β − ES α − E ⎥⎦ ⎢⎣ cB ⎥⎦ ⎣ 0 ⎦

All overlap integrals are set equal to zero.

All resonance integrals between non-neighbours 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 = cA A + cB B =0 = 0 → Secular Equation
∂cA ∂cB
⎧α A = AĤA dτ ( ≠ Eo why?∵S ≠ 0 ) → Coulomb Integral = HJJ
⎪ ∫
∂E
= 0 → (α A − E ) cA + ( β − ES ) cB = 0 ⎪α B = BĤB dτ → Coulomb Integral
∂cA ⎪ ∫
⎨
∂E ⎪β = ∫ BĤA dτ = ∫ AĤB dτ → Resonance (Hopping) Integral
= 0 → ( β − ES ) cA + (α B − E ) cB = 0 ⎪
∂cB
⎪⎩S = ∫ BA dτ = ∫ AB dτ → Overlap Integral = SAB, SJJ=1

⎡ α A − E β − ES ⎤ ⎡ cA ⎤ ⎡ 0 ⎤
⎢ ⎥⎢ ⎥=⎢ ⎥ ( H AA − ESAA ) cA + ( H AB − ESAB ) cB = 0
⎢⎣ β − ES α B − E ⎥⎦ ⎢⎣ cB ⎥⎦ ⎣ 0 ⎦
( H BA − ESBA ) cA + ( H BB − ESBB ) cB = 0 J = A, B
i = 1, 2
⎛⎡ H H AB ⎤ ⎡ SAA SAB ⎤⎞ ⎡ ci,A ⎤
=⎜⎢
AA

⎜⎝ ⎢ H BA
⎥ − Ei ⎢ ⎥⎟ ⎢
SBB ⎥⎟⎠ ⎢ ci,B
⎥=0 ( H AA − Ei SAA ) ci,A + ( H AB − Ei SAB ) ci,B = 0
⎣
H BB ⎥
⎦ ⎢⎣ SBA ⎦ ⎣ ⎥⎦
( H BA − Ei SBA ) ci,A + ( H BB − Ei SBB ) ci,B = 0
( )
= H! − Ei S! c!i = 0 → Hc
! = S!c! E
i i i
⎡ H AA − Ei SAA H AB − Ei SAB ⎤ ⎡ ci,A ⎤
⎢ ⎥⎢ ⎥=0
⎡ c1,A c2,A ⎤ ⎡ E1 0 ⎤ ⎢⎣ H BA − Ei SBA H BB − Ei SBB ⎥ ⎢ ci,B ⎥⎦
c! = ⎢ ⎥ E=⎢ ⎥ ⎦⎣
⎢⎣ c1,B c2,B ⎥⎦ ⎢⎣ 0 E2 ⎥
⎦
→ H! c! = S!c!E!
 The Matrix Formulation of the Hückel
Method
∂E ∂E
Ψ = cA A + cB B =0 = 0 → Secular Equation
∂cA ∂cB
⎧α A = AĤA dτ ( ≠ Eo why?∵S ≠ 0 ) → Coulomb Integral = HJJ
⎪ ∫
⎪α = BĤB dτ → Coulomb Integral
⎪ B ∫
⎡ H AA − Ei SAA H AB − Ei SAB ⎤ ⎡ ci,A ⎤
⎨ ⎢ ⎥⎢ ⎥=0
⎪β = ∫ BĤA dτ = ∫ AĤB dτ → Resonance (Hopping) Integral ⎢⎣ H BA − Ei SBA H BB − Ei SBB ⎥ ⎢ ci,B
⎦⎣ ⎥⎦
⎪
⎪⎩S = ∫ BA dτ = ∫ AB dτ → Overlap Integral = SAB, SJJ=1

⎛⎡ 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!
⎢⎣ 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.

⎡ H 14 ⎤ ⎧α A = AĤA dτ ( ≠ Eo why?∵S ≠ 0 ) → Coulomb Integral

⎢
H 11 H 12 H 13
⎥ ⎪ ∫
⎪α B = BĤB dτ → Coulomb Integral
! ⎢
H=⎢
H 21 H 22 H 23 H 24 ⎥ ⎪ ∫
⎨
H 31 H 32 H 33 H 34 ⎥ ⎪β = ∫ BĤA dτ = ∫ AĤB dτ → Resonance (Hopping) Integral
⎢ ⎥ ⎪
⎢⎣ H 41 H 42 H 43 H 44 ⎥ ⎪⎩S = ∫ BA dτ = ∫ AB dτ → Overlap Integral
⎦

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: Eextra 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