Subject PHYSICAL CHEMISTRY

Paper No and Title 2, PHYSICAL CHEMISTRY-II

TOPIC QUANTUM CHEMISTRY

Sub-Topic (if any) Hückel Molecular orbital Theory – Application PART IV

Module No. 34

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 TABLE OF CONTENTS
1. Learning outcomes
2. Hückel Molecular Orbital (HMO) Theory
3. Application of HMO theory

3.1 Cyclobutadiene

4. Summary

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 1. Learning Outcomes
After studying this module, you shall be able to

 Find the π-electron energy and wavefunction for cyclobutadiene

 Understand the basis of molecular orbital diagram for π-electron systems

2. Hückel Molecular orbital theory

HMO theory is an approximate theory that gives a quick picture of the molecular orbital
energy diagram of organic conjugated molecules. The Hückel theory treats only π-
electrons in a planar conjugated molecule. HMO calculations are carried out using
variation method and LCAO(π)-MO approximation. The basis set for MO approximation
consists of one pπ-orbital on each atom. The σ skeleton of the conjugated molecule is
assumed frozen and no σ-π interactions are considered in this study. In addition, electron-
electron repulsions are neglected in π-Hamiltonian of conjugated molecule.
Note: In this module, we have consistently assumed the plane of the molecule as x-y
plane with π orbital in the z axis, perpendicular to the molecular plane.

According to LCAO-MO approximation, the MO is written as,

𝝋𝒂 = ∑𝒏𝒊=𝟏 𝒄𝒊 𝝍𝟐𝒑𝒛 𝒊 -(1)

And the approximate energy is given by,

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 ∫ φ*a H
̂ φa dτ
Ea = * ≥ Eo -(2)
∫ φa φa dτ

A trial function that depends linearly on the variational parameters leads to a secular determinant
which gives secular equation as an approximation to the energy.
𝑯𝟏𝟏 − 𝑬𝑺𝟏𝟏 … … . 𝑯𝟏𝒏 − 𝑬𝑺𝟏𝒏
| ……. ……. ……. |=𝟎 -(3)
𝑯𝒏𝟏 − 𝑬𝑺𝒏𝟏 … … . 𝑯𝒏𝒏 − 𝑬𝑺𝒏𝒏
To solve the Secular determinant for an n-π electron system, Hückel treated the Hii , Hij,
Sij and Sij integrals as parameters that can be evaluated empirically by fitting the theory to
experimental results.
̂ 𝝍𝒋 𝒅𝝉
1. 𝑯𝒊𝒋 = ∫ 𝝍∗𝒊 𝑯
𝜶 (𝒊 = 𝒋) 𝑪𝒐𝒖𝒍𝒐𝒎𝒃 𝒊𝒏𝒕𝒆𝒈𝒓𝒂𝒍 -(3)
𝑯𝒊𝒋 = {
𝜷 (𝒊 ≠ 𝒋) 𝑹𝒆𝒔𝒐𝒏𝒂𝒏𝒄𝒆 𝒊𝒏𝒕𝒆𝒈𝒓𝒂𝒍

2. 𝑺𝒊𝒋 = ∫ 𝝍∗𝒊 𝝍𝒋 𝒅𝝉
𝟏 (𝒊 = 𝒋) -(4)
𝑺𝒊𝒋 = { 𝑶𝒗𝒆𝒓𝒍𝒂𝒑 𝒊𝒏𝒕𝒆𝒈𝒓𝒂𝒍
𝟎 (𝒊 ≠ 𝒋)

The expansion of an n x n Hückel determinant yields a polynomial equation which has n

real roots which n-π electron system has n energy levels and n molecular orbitals. The
energy of any ath molecular orbital (MO) is given by

𝑬𝒂 = 𝜶 + 𝒙𝒂 𝜷, 𝒘𝒉𝒆𝒓𝒆 𝒙𝒂 𝒊𝒔 𝒕𝒉𝒆 𝒂𝒕𝒉 𝒓𝒐𝒐𝒕 𝒐𝒇 𝒕𝒉𝒆 𝒑𝒐𝒍𝒚𝒏𝒐𝒎𝒊𝒂𝒍 -(5)

3. Application of HMO theory

In this section, we shall apply HMO theory to a cyclic conjugated molecule viz.,
cyclobutadiene.

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 3.1 Cyclobutadiene

Now, we will consider the treatment of cyclobutadiene molecule using HMO theory in
detail.

Cyclobutadiene is a 4 π-electron cyclic system where the carbon atoms are adjacent with
each carbon 2pz orbital contributes 1 electron to the HMO π-electron system.

The four atomic orbitals (AOs) combine to form molecular orbitals (MOs).

Labeling the four carbons as 1, 2, 3 and 4,

The Hückel molecular orbital wavefunction for this system becomes

𝜑𝑎 = 𝑐1 𝜓2𝑝𝑧1 + 𝑐2 𝜓2𝑝𝑧2 + 𝑐3 𝜓2𝑝𝑧3 + 𝑐4 𝜓2𝑝𝑧4 -(6)

The Secular equations obtained for cyclobutadiene molecule are of the form:
(H11 − ES11 )𝑐1 + (H12 − ES12 )𝑐2 + (H13 − ES13 )𝑐3 + (H14 − ES14 )𝑐4 = 0
(H21 − ES21 )𝑐1 + (H22 − ES22 )𝑐2 + (H23 − ES23 )𝑐3 + (H24 − ES24 )𝑐4 = 0
CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I
MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 (H31 − ES31 )𝑐1 + (H32 − ES32 )𝑐2 + (H33 − ES33 )𝑐3 + (H34 − ES34 )𝑐4 = 0
(H41 − ES41 )𝑐1 + (H42 − ES42 )𝑐2 + (H43 − ES43 )𝑐3 + (H44 − ES44 )𝑐4 = 0
which can be written in the form of secular determinant as,
𝐻11 − 𝐸𝑆11 𝐻12 − 𝐸𝑆12 𝐻13 − 𝐸𝑆13 𝐻14 − 𝐸𝑆14 𝑐1
𝐻 − 𝐸𝑆21 𝐻22 − 𝐸𝑆22 𝐻23 − 𝐸𝑆23 𝐻24 − 𝐸𝑆24 𝑐2
[ 21 ][ ] = 0 -(7)
𝐻31 − 𝐸𝑆31 𝐻32 − 𝐸𝑆32 𝐻33 − 𝐸𝑆33 𝐻34 − 𝐸𝑆34 𝑐3
𝐻41 − 𝐸𝑆41 𝐻42 − 𝐸𝑆42 𝐻43 − 𝐸𝑆43 𝐻44 − 𝐸𝑆44 𝑐4

In this case, carbon atom 1 is connected to carbon atom 4, i.e., the C1 and C4 are
neighbors.

Taking into account the assumptions of HMO theory, the secular determinant transforms
into Hückel determinant as,
𝐻11 = 𝐻22 = 𝐻33 = 𝐻44 = 𝛼
𝐻12 = 𝐻21 = 𝐻23 = 𝐻32 = 𝐻34 = 𝐻43 = 𝐻14 = 𝐻41 = 𝛽
𝐻13 = 𝐻31 = 𝐻24 = 𝐻42 = 0 𝑆11 = 𝑆22 = 𝑆33 = 𝑆44 = 1
𝑆12 = 𝑆21 = 𝑆13 = 𝑆31 = 𝑆14 = 𝑆41 = 𝑆23 = 𝑆32 = 𝑆24 = 𝑆42 = 𝑆34 = 𝑆43 = 0

𝜶 − 𝑬 𝜷 𝟎 𝜷 𝑐1
𝜷 𝜶 − 𝑬 𝜷 𝟎 𝑐2
[ ][ ] = 0
𝟎 𝜷 𝜶 − 𝑬 𝜷 𝑐3 -(8)
𝜷 𝟎 𝜷 𝜶 − 𝑬 𝑐4

𝑐1 𝜶−𝑬 𝜷 𝟎 𝜷
𝑐2 𝜷 𝜶−𝑬 𝜷 𝟎
[𝑐 ] ≠ 0 ⇒ [ ]=0
3 𝟎 𝜷 𝜶−𝑬 𝜷
𝑐4 𝜷 𝟎 𝜷 𝜶−𝑬

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 𝜶−𝑬 𝜷 𝟎 𝜷
𝜷 𝜶−𝑬 𝜷 𝟎
| |=0 -(9)
𝟎 𝜷 𝜶−𝑬 𝜷
𝜷 𝟎 𝜷 𝜶−𝑬

𝛼−𝐸
Let, 𝜆 = -(10)
𝛽

This reduces the Hückel determinant as,

𝝀 𝟏 𝟎 𝟏
𝟏 𝝀 𝟏 𝟎
| |=0 -(11)
𝟎 𝟏 𝝀 𝟏
𝟏 𝟎 𝟏 𝝀

The Hückel determinant leads to a polynomial equation,

𝑥 4 − 4𝑥 2 = 0 -(12)
Thus, we have the roots of the polynomial equation as,
𝜆1 = −2; 𝜆2 = 0; 𝜆3 = 0; 𝜆4 = 2 -(13)

So, the energies of the molecular orbitals of cyclobutadiene are of the form,

𝜆1 = −2 𝐸1 = 𝛼 + 2𝛽 -(14)
𝜆2 = 𝜆3 = 0 𝐸2 = 𝐸3 = 𝛼 -(15)
𝜆4 = 2 𝐸4 = 𝛼 − 2𝛽 -(16)

The two energy levels viz., E2 and E3 are degenerate (doubly degenerate non-bonding
levels).
The Hückel energy level diagram for cyclobutadiene is shown below:

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 𝑇𝑜𝑡𝑎𝑙 𝜋 𝑒𝑛𝑒𝑟𝑔𝑦 (𝐸𝜋 ) = 2(𝛼 + 2𝛽) + 2𝛼 = 4𝛼 + 4𝛽 -(17)

𝐸𝐷.𝐸. = 𝐸𝜋 − 𝐸𝑒𝑡ℎ𝑦𝑙𝑒𝑛𝑒 = 4𝛼 + 4𝛽 − 4𝛼 − 4𝛽 = 0 -(18)

Delocalization energy for cyclobutadiene is zero which indicates that there is no

additional stability in the molecule by delocalization. (The ring is small and is under
strain which is not compensated by delocalization making it difficult to synthesize)

Now, we solve for HMO coefficients,

𝛼−𝐸
In terms of λ which is taken as 𝜆 = , the secular equations for cyclobutadiene are as
𝛽
follows,

𝝀 𝟏 𝟎 𝟏 𝑐1
𝟏 𝝀 𝟏 𝟎 𝑐2 -(19)
[ ][ ] = 0
𝟎 𝟏 𝝀 𝟏 𝑐3
𝟏 𝟎 𝟏 𝝀 𝑐4

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 𝜆𝑐1 + 𝑐2 + 0 + 𝑐4 = 0

𝑐1 + 𝜆𝑐2 + 𝑐3 + 0 = 0
-(20)
0 + 𝑐2 + 𝜆𝑐3 + 𝑐4 = 0

𝑐1 + 0 + 𝑐3 + 𝜆𝑐4 = 0

We now solve the above set of equations by the method of elimination.

𝐹𝑜𝑟, 𝜆 = −2, the secular equations become

−2𝑐1 + 𝑐2 + 0 + 𝑐4 = 0 -(21)

𝑐1 − 2𝑐2 + 𝑐3 + 0 = 0 -(22)

0 + 𝑐2 − 2𝑐3 + 𝑐4 = 0 -(23)

𝑐1 + 0 + 𝑐3 − 2𝑐4 = 0 -(24)

Subtracting equation (23) from equation (21) gives,

−2𝑐1 + 2𝑐3 = 0 -(25)

𝑐1 = 𝑐3 -(26)

Multiplying equation (24) by 2 and then subtracting it from equation (25) gives,
−4𝑐1 + 4𝑐4 = 0 -(27)

𝑐1 = 𝑐4 -(28)

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 Now, one can eliminate c4 from equation (21) by multiplying it by 4 and then subtracting
equation (27) from it,

−4𝑐1 + 4𝑐2 = 0 -(29)

𝑐1 = 𝑐2 -(30)

The sum of squares of coefficients is always unity, i.e., from normalization condition we
have,

𝑐1 2 + 𝑐2 2 + 𝑐3 2 + 𝑐4 2 = 1 -(31)

Now, using equations (26), (28) and (30), we get normalization condition for 𝜆 = −2 as,

4𝑐1 2 = 1 𝑜𝑟 𝑐1 = 𝑐2 = 𝑐3 = 𝑐4 = 1⁄ = 1⁄2 -(32)

√4

So, we get the wavefunction corresponding to 𝜆 = −2 as,

𝜑1 = 1⁄2 (𝜓2𝑝𝑧1 + 𝜓2𝑝𝑧2 + 𝜓2𝑝𝑧3 + 𝜓2𝑝𝑧4 ) -(33)

𝐹𝑜𝑟, 𝜆 = 0 (corresponding to degenerate energy levels viz., E2 and E3), the secular
equations become
0𝑐1 + 𝑐2 + 0 + 𝑐4 = 0

𝑐1 + 0𝑐2 + 𝑐3 + 0 = 0
-(34)
0 + 𝑐2 + 0𝑐3 + 𝑐4 = 0

𝑐1 + 0 + 𝑐3 + 0𝑐4 = 0

The value of the coefficients corresponding to 𝜆 = 0 cannot be determined using the

above set of equations alone. We know that the energy levels corresponding to 𝜆 =

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 0 (𝐸2 𝑎𝑛𝑑 𝐸3 ) are degenerate. And in case of degenerate orbitals, HMO method cannot
determine the coefficients uniquely. One can choose any value for c1, c2, c3 and c4
provided that they satisfy the conditions of normalization and orthogonality as well as the
values of c1, c2, c3 and c4 must satisfy the above set of equations.
A simple method to satisfy the above mentioned three conditions is to set any one of the
coefficients equal to zero. Let 𝑐2 = 0, then we have from equation (34),
𝑐4 = 0
-(35)
𝑐1 = −𝑐3

From normalization condition,

𝑐1 2 + 𝑐2 2 + 𝑐3 2 + 𝑐4 2 = 1

𝑐1 2 + 𝑐3 2 = 1

2𝑐1 2 = 1

𝑐1 = 1⁄ -(36)
√2

𝑐3 = − 1⁄ -(37)
√2

So, we get the wavefunction corresponding to 𝜆 = 0 as,

𝜑2 = 1⁄ (𝜓2𝑝𝑧1 − 𝜓2𝑝𝑧3 ) -(38)

√2

We arbitrarily chose 𝑐2 = 0 or in other words φ2 but we cannot repeat the same process
for determining φ3. This is because φ3 must be orthogonal to φ1 , φ2 and φ4.
-(39)
∫ 𝜑1 𝜑3 𝑑𝜏 = 0

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 -(40)
∫ 𝜑2 𝜑3 𝑑𝜏 = 0

-(41)
∫ 𝜑3 𝜑4 𝑑𝜏 = 0

Note: We can choose any equation (from 39, 40 & 41) for finding φ3 as HMO
method cannot determine the coefficients uniquely.

For instance, taking equation (40), we get

∫ [1⁄ (𝜓2𝑝𝑧1 − 𝜓2𝑝𝑧3 )] [𝑐1 𝜓2𝑝𝑧1 + 𝑐2 𝜓2𝑝𝑧2 + 𝑐3 𝜓2𝑝𝑧3 + 𝑐4 𝜓2𝑝𝑧4 ]𝑑𝜏 = 0 -(42)
√2

On expanding the equation (42) we get,

∫ [1⁄ 𝑐1 𝜓2𝑝𝑧1 2 + 1⁄ 𝑐2 𝜓2𝑝𝑧1 𝜓2𝑝𝑧2 + 1⁄ 𝑐2 𝜓2𝑝𝑧1 𝜓2𝑝𝑧3 + 1⁄ 𝑐2 𝜓2𝑝𝑧1 𝜓2𝑝𝑧4

√2 √2 √2 √2
− 1⁄ 𝑐1 𝜓2𝑝𝑧1 𝜓2𝑝𝑧3 − 1⁄ 𝑐2 𝜓2𝑝𝑧2 𝜓2𝑝𝑧3 − 1⁄ 𝑐3 𝜓2𝑝𝑧3 2
√2 √2 √2

− 1⁄ 𝑐4 𝜓2𝑝𝑧4 𝜓2𝑝𝑧3 ] 𝑑𝜏 = 0
√2

∫ [1⁄ 𝑐1 𝜓2𝑝𝑧1 2 − 1⁄ 𝑐3 𝜓2𝑝𝑧3 2 ] 𝑑𝜏 = 0

√2 √2

1⁄ 𝑐 − 1⁄ 𝑐 = 0
1 3
√2 √2
CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I
MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 𝑐1 = 𝑐3 -(43)

But 𝑐1 + 𝑐3 = 0, from equation (34)

⇒ 𝑐1 = 𝑐3 = 0
𝑆𝑖𝑛𝑐𝑒 𝑐2 + 𝑐4 = 0 ⇒ 𝑐2 = −𝑐4

From normalization condition,

𝑐1 2 + 𝑐2 2 + 𝑐3 2 + 𝑐4 2 = 1

𝑐2 2 + 𝑐4 2 = 1

2𝑐2 2 = 1

𝑐2 = 1⁄ -(44)
√2

𝑐4 = − 1⁄ -(45)
√2

So, we get the wavefunction corresponding to 𝜆 = 0 (degenerate with φ2) as,

𝜑3 = 1⁄ (𝜓2𝑝𝑧2 − 𝜓2𝑝𝑧4 ) -(46)

√2

𝐹𝑜𝑟, 𝜆 = 2, the secular equations become

2𝑐1 + 𝑐2 + 0 + 𝑐4 = 0 -(47)

𝑐1 + 2𝑐2 + 𝑐3 + 0 = 0 -(48)

0 + 𝑐2 + 2𝑐3 + 𝑐4 = 0 -(49)

𝑐1 + 0 + 𝑐3 + 2𝑐4 = 0 -(50)
CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I
MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 Subtracting equation (49) from equation (47) gives,
2𝑐1 − 2𝑐3 = 0 -(51)

𝑐1 = 𝑐3 -(52)

Multiplying equation (50) by 2 and then adding it to equation (51) gives,

4𝑐1 + 4𝑐4 = 0 -(53)

𝑐1 = −𝑐4 -(54)

Now, one can eliminate c4 from equation (47) by multiplying it by 4 and then subtracting
equation (53) from it,

4𝑐1 + 4𝑐2 = 0 -(55)

𝑐1 = −𝑐2 -(56)

From normalization condition,

𝑐1 2 + 𝑐2 2 + 𝑐3 2 + 𝑐4 2 = 1

Now, using equations (52), (54) and (56), we get normalization condition for 𝜆 = 2 as,

4𝑐1 2 = 1 𝑜𝑟 𝑐1 = 1⁄ = 1⁄2 -(57)

√4

𝑐3 = 1⁄2 -(58)

𝑐2 = 𝑐4 = − 1⁄2 -(59)

So, we get the wavefunction corresponding to 𝜆 = 2 as,

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I
MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 𝜑4 = 1⁄2 (𝜓2𝑝𝑧1 − 𝜓2𝑝𝑧2 + 𝜓2𝑝𝑧3 − 𝜓2𝑝𝑧4 ) -(60)

The pictorial representation of the four Hückel molecular orbitals for cyclobutadiene is
shown below:

 Electron density:

The total electron density is taken as the sum of electron densities contributed by
different electron in each HMO
2
𝑞𝑛 = ∑ 𝑛𝑖 𝑐𝑖𝑛 𝑛𝑖 𝑖𝑠 𝑡ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑖𝑛 𝑖𝑡ℎ 𝐻𝑀𝑂 (0,1 𝑜𝑟 2)
𝑖

In case of cyclobutadiene, two π-electrons are in energy state E1 while the third and
fourth electrons singly occupy degenerate energy states E2 and E3.

2 2 2
𝑞1 = 2 × (1⁄2) + 1 × (1⁄ ) + 1 × 0 + 0 × (1⁄2) = 1
√2

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 2 2 2
𝑞2 = 2 × (1⁄2) + 1 × 0 + 1 × (1⁄ ) + 0 × (− 1⁄2) = 1
√2

2 2 2
𝑞3 = 2 × (1⁄2) + 1 × (− 1⁄ ) + 1 × 0 + 0 × (1⁄2) = 1
√2

2 2 2
𝑞4 = 2 × (1⁄2) + 1 × 0 + 1 × (− 1⁄ ) + 0 × (− 1⁄2) = 1
√2

 Charge density
In a conjugated molecule, a neutral carbon is associated with an electron density of
1.0 and the net charge density is defined as
𝜀𝑛 = 1 − 𝑞𝑛
For cyclobutadiene,
𝜀1 = 1 − 1 = 0 = 𝜀2 = 𝜀3 = 𝜀4
 Π-bond order between adjacent carbon atoms is given by
𝜋
𝐵𝑂𝑎𝑏 = ∑ 𝑛𝑖 𝑐𝑖𝑎 𝑐𝑖𝑏
𝑖

𝑤ℎ𝑒𝑟𝑒 𝑛𝑖 𝑖𝑠 𝑡ℎ𝑒 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝜋 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑖𝑛 𝑖𝑡ℎ 𝑀𝑂

𝑐𝑖𝑎 𝑐𝑖𝑏 𝑖𝑠 𝑡ℎ𝑒 𝜋 − 𝑒𝑙𝑒𝑐𝑡𝑜𝑟𝑛 𝑐ℎ𝑎𝑟𝑔𝑒 𝑖𝑛 𝑖𝑡ℎ 𝑀𝑂 𝑏𝑒𝑡𝑤𝑒𝑒𝑛 𝑎𝑑𝑗𝑎𝑐𝑒𝑛𝑡
𝑐𝑎𝑟𝑏𝑜𝑛 𝑎𝑡𝑜𝑚𝑠 𝑎 𝑎𝑛𝑑 𝑏

For cyclobutadiene,
𝜋
𝐵𝑂12 = (2 × 1⁄2 × 1⁄2) + (1 × 1⁄ × 0) + (1 × 0 × 1⁄ )
√2 √2
𝜋
𝐵𝑂12 = 0.5

𝜋
𝐵𝑂23 = (2 × 1⁄2 × 1⁄2) + (1 × 0 × − 1⁄ ) + (1 × 1⁄ × 0)
√2 √2
𝜋
𝐵𝑂23 = 0.5

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
 𝜋
𝐵𝑂34 = (2 × 1⁄2 × 1⁄2) + (1 × − 1⁄ × 0) + (1 × 0 × − 1⁄ )
√2 √2
𝜋
𝐵𝑂31 = 0.5

𝜋
𝐵𝑂41 = (2 × 1⁄2 × 1⁄2) + (1 × 0 × 1⁄ ) + (1 × − 1⁄ × 0)
√2 √2
𝜋
𝐵𝑂41 = 0.5

This implies that all the bonds in cyclobutadiene are neither single bonds nor double
bonds. All the bonds have character intermediate between single and double bonds.

4. Summary

 HMO theory is an approximate theory that gives a quick picture of the molecular
orbital energy diagram of organic conjugated molecules.
 The Hückel theory treats only π- electrons in a planar conjugated molecule. HMO
calculations are carried out using variation method and LCAO(π)-MO approximation.
 The basis set for MO approximation consists of one pπ-orbital on each atom.
 Application of HMO theory to cyclobutadiene
 Cyclobutadiene is a four electron system
 𝐸1 = 𝛼 + 2𝛽 𝐸2 = 𝐸3 = 𝛼 𝐸4 = 𝛼 − 2𝛽
The two energy levels viz., E2 and E3 are degenerate.
 𝐸𝜋 = 4𝛼 + 4𝛽
 𝐸𝐷.𝐸. = 0
Delocalization energy for cyclobutadiene is zero which indicates that there is no
additional stability in the molecule by delocalization. (The ring is small and is under
strain which is not compensated by delocalization making it difficult to synthesize)
CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I
MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV
  𝜑1 = 1⁄2 (𝜓2𝑝𝑧1 + 𝜓2𝑝𝑧2 + 𝜓2𝑝𝑧3 + 𝜓2𝑝𝑧4 )

𝜑2 = 1⁄ (𝜓2𝑝𝑧1 − 𝜓2𝑝𝑧3 )
√2
𝜑3 = 1⁄ (𝜓2𝑝𝑧2 − 𝜓2𝑝𝑧4 )
√2
𝜑4 = 1⁄2 (𝜓2𝑝𝑧1 − 𝜓2𝑝𝑧2 + 𝜓2𝑝𝑧3 − 𝜓2𝑝𝑧4 )
 All the bonds in cyclobutadiene are neither single bonds nor double bonds. All the
bonds have character intermediate between single and double bonds.

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 34, Hückel Molecular orbital Theory –
Application PART IV