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Subject PHYSICAL CHEMISTRY

Paper No and Title 2, PHYSICAL CHEMISTRY-II

TOPIC QUANTUM CHEMISTRY

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

Module No. CHE_P2_M31

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 31, Hückel Molecular orbital Theory –
Application PART I
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TABLE OF CONTENTS
1. Learning outcomes
2. Hückel Molecular Orbital (HMO) Theory
3. Application of HMO theory

3.1 Ethylene

4. Summary

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 31, Hückel Molecular orbital Theory –
Application PART I
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1. Learning Outcomes
After studying this module, you shall be able to

 Appreciate the simplification introduced by E Hückel for studying organic conjugated

molecules.
 Find the π-electron energy and wave function for ethylene molecule
 Understand the basis of molecular orbital diagram for π-electron systems

2. Hückel Molecular orbital (HMO) theory

HMO theory is an approximate method which simplifies variation method to treat planar
conjugated hydrocarbons. This theory treats the π electrons separately from σ electrons.
Properties of the conjugated molecules are primarily determined by π-electrons. The
consideration of σ-π electro separation in a multi-electron molecule in HMO theory
reduces the problem to the study of only π electrons. HMO calculations are carried out
using variation method and LCAO(π)-MO approximation.

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

n
 a   ci 2 p i
z
-(1)
i 1

HMO theory approximates the π molecular orbitals as linear combination of atomic

orbitals. For a planar conjugated hydrocarbon, the only atomic orbitals of π symmetry are
the 2pπ orbtials on carbon. 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.

For a two π electron system φa becomes,

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MODULE: 31, Hückel Molecular orbital Theory –
Application PART I
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  c   c 
a 1 2 pz 1 2 2 pz 2 -(2)

And the approximate energy is given by,

^

  H  d
*


a a
Ea -(3)
   d
*
a a

The Hamiltonian Ĥ incorporates the effect of the interaction of π electron with the rest of
the molecule (nuclei, inner electrons, σ bonds) in an average way In HMO method, π
electrons are assumed to be moving in a potential generated by the nuclei and σ electrons
of the molecule.
The Secular determinant obtained for two π electron system can be written as,

 H 11  ES11 H 12  ES12   c1 
 H  ES 0
H 22  ES 22  c 2 
-(4)
 21 21

In order 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.
^
1. H ij   2 p z i H  2 pz j d
*

 (i  j ) Coulomb integral
H ij  
 (i  j ) Resonance integral

2. S ij   2 pzi  2 pz j d
*

1 (i  j ) Overlap integral
S ij  
0 (i  j )

Taking into account the assumptions of HMO theory, the secular determinant reduces to,

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MODULE: 31, Hückel Molecular orbital Theory –
Application PART I
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 E 
0 -(5)
  E

In this manner, Hückel determinant can be generated for an n-π electron system

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

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

E a    x a  , where xais the ath root of the polynomial. -(6)

The values of the coulomb integral α and the resonance integral β are always negative. If
the root xa is positive, then the energy level corresponds to a more negative value and is
more stable (Bonding molecular orbital) while a negative value of root gives antibonding
molecular orbital.

3. Application of HMO theory

In this section, we shall apply HMO theory to ethylene having 2 π electrons with one
double bond.

3.1 Ethylene

We consider here the case of ethylene, C2H4.

Ethylene is a 16 electron system but HMO theory reduces this to a two π electron system.

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 31, Hückel Molecular orbital Theory –
Application PART I
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HMO theory treats ethylene as a two electron problem, with one π electron on each
carbon atom in p-orbital, perpendicular to the molecular plane. These two atomic orbitals
(AOs) combine to form molecular orbitals (MOs).

Labeling the two carbons as 1 and 2,

The Secular determinant obtained for ethylene molecule is of the form,

 a  c1 2 pz1  c2 2 pz 2 -(7)

 H 11  ES11 H 12  ES12   c1 
 H  ES 0
H 22  ES 22  c 2 
-(8)
 21 21

Taking into account the assumptions of HMO theory, the secular determinant transforms
into Hückel determinant as,

H 11  H 22   H 12  H 21  
S11  S 22  1 S12  S 21  0

1  E 12   c1 
  0
 21   E  c2 

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MODULE: 31, Hückel Molecular orbital Theory –
Application PART I
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 c1    E  
c   0    0
 2    E 

 E 
0 -(9)
  E

 E
Let, 

-(10)

This reduces the Hückel determinant as,

 1
0
1  -(11)

which on expansion gives,

2  1  0
  1 -(12)

So, the energies of the molecular orbitals are,

If   1, E     ( Bonding Molecular Orbital BMO)

If   1, E     ( Antibonding Molecular Orbital ABMO)

The number of molecular orbitals that are generated using LCAO approximation are equal to
the number of combining atomic orbitals.

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MODULE: 31, Hückel Molecular orbital Theory –
Application PART I
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HMO energy level diagram for ethylene

Total (π bond) energy = 2(α + β) -(13)

[As there are two electrons in the orbital with energy α+β]

 E
Using λ as 
 ,
the secular equations are obtained as

 1   c1 
 1   c   0 -(14)
  2 

c1  c2  0
-(15)
c1  c2  0

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MODULE: 31, Hückel Molecular orbital Theory –
Application PART I
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If   1, c1  c 2
-(16)
If   1, c1  c 2

 c1  c 2  c -(17)

Now, if we apply the normalization condition,

  d  1
*
a a -(18)

 (c 
1 2 pz1  c2 2 pz 2 ) 2 d  1

c 2  ( 2 pz1  2 pz 2 ) 2 d  1
If i = j, ψi2 = 1
c 2  ( 2 pz1  2 pz 2  2 2 pz1 2 pz 2 )d  1
2 2

If i ≠ j, ψi2 = 0

 c 2 [1  1  0]  1

1
c -(19)
2

The sum of the squares of the coefficients is always unity.

Molecular λ E c1 c2 Number of
orbital nodes
BMO -1 α+β 1 1 0
c c
2 2
ABMO 1 α-β 1 1 1
c c
2 2

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MODULE: 31, Hückel Molecular orbital Theory –
Application PART I
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With this, one can now write the two normalized wavefunctions corresponding to two
Hückel molecular orbitals for ethylene as,

1
 BMO  ( 2 pz1   2 pz 2 ) -(20)
2
1
 ABMO  ( 2 pz1   2 pz 2 ) -(21)
2

The pictorial representation of the two Hückel molecular orbitals viz., BMO and ABMO
for ethylene is shown below.

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MODULE: 31, Hückel Molecular orbital Theory –
Application PART I
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The total π electron energy (or π electron binding energy) Eπ is taken as the sum of the
energies corresponding to each π electron. For ethylene, the total π electron energy Eπ is
given by
E  2  2 -(22)

Another related term is π bond formation energy which is the energy released when a π
bond is formed. Since the contribution of α is same in the molecules as in the atoms, so
we can consider the energy of two electrons, each one in isolated and non-interacting
atomic orbitals as 2α, then the π bond formation energy becomes,
E (bond formation)  E  Eisolated -(23)

In general,

E (bond formation)  E  n , where n  number of C atoms in the molecule

For ethylene,

E (bond formation)  2  2  2  2
-(24)

2β is the total π bonding energy on formation of the ethylene molecule.

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MODULE: 31, Hückel Molecular orbital Theory –
Application PART I
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4. Summary

 HMO theory is an approximate method which simplifies variation method to treat

planar conjugated hydrocarbons
 This theory treats the π electrons separately from σ electrons.
 Properties of the conjugated molecules are primarily determined by π-electrons.
 HMO calculations are carried out using variation method and LCAO(π)-MO
approximation
 Application of HMO theory to ethylene molecule
 Ethylene is a 16 electron system but HMO theory reduces this to a two π electron
system.

1
  BMO  ( 2 pz1   2 pz 2 )
2
1
 ABMO  ( 2 pz1   2 pz 2 )
2
 E  2  2

Molecular λ E c1 c2 Number of
orbital nodes
BMO -1 α+β 1 1 0
c c
2 2
ABMO 1 α-β 1 1 1
c c
2 2

CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 31, Hückel Molecular orbital Theory –
Application PART I
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CHEMISTRY PAPER:2, PHYSICAL CHEMISTRY-I

MODULE: 31, Hückel Molecular orbital Theory –
Application PART I