HUCKEL MOLECULAR ORBITAL THEORY

Sapan Kumar Jain

Assistant Professor, JMI
2
nd
3 weeks Referesher Course
J AMIA MILIA ISLAMIA
Particle in a box, the harmonic oscillator, the hydrogen
atom, Helium ion are all exactly solvable problems.

But when we encounter larger systems, detailed and
accurate solutions become much more difficult to
perform and interpret,
Hckel Theory (Erich Hckel) E. Hckel, Z. Physik, 1931, 70, 204.
Illustration of LCAO approach formulated in the early 1930s
Used to describe unsaturated/aromatic hydrocarbons
The Hckel model has been largely superseded by more accurate MO calculations.
However, it is still useful to obtain qualitative predictions of bonding and reactivity in
conjugated tsystems.
Hckel Molecular Orbital Theory
Variation Theorem :

The significance of the variation theorem is that the trial function giving the lowest
Rayleigh ratio is the optimum function of that form. Moreover, because the Rayleigh ratio
is not less than the true ground-state energy of the system, we have a way of calculating
an upper bound to the true energy of the system. Typically, the trial function is expressed
in terms of one or more parameters that are varied until the Rayleigh ratio is minimized.
If +
trial
= p
1
|
1
+ p
2
|
2

where |1 are |2 are suitable
arbitary orthonormal trial functions

The variation principle seeks the
values of the parameters (two are
shown here) that minimize the
energy. The resulting wavefunction
is the optimum wavefunction of the
selected form.


0
1
=
c
c
p
E

0
2
=
c
c
p
E
Huckel theory begins with 2 Structural Assumptions:
1. The electrons of interest initially occupy a system of carbon 2p orbitals having a
common nodal plane; that is, with their long axes parallel; they interact to form t-type
molecular orbitals;
2. The rest of the electrons in the molecule occupy a o-orbital framework that is
orthogonal to the 2p orbitals and therefore does not interact with them.




The description of Hckel theory as an LCAO method means that it assumes that
t-molecular orbitals, +, can be represented as a linear combination of atomic orbitals, |
(basis set):



where
j is an index over molecular orbitals (MOs)
n is an index over atomic orbitals (Aos)
c is a set of coefficients weighting the contributions of the atomic orbitals to the
molecular orbitals
The wave functions, +, are called one-electron wave functions:

They represent the motion of a single electron in the electric field provided
by the nuclei and the averaged distribution of the other electrons.

Because they take account of the other electrons only in an average, they
do not account properly for electron correlation, the tendency of electrons to
avoid each other insofar as possible.
This problem is particularly severe for paired electrons in the same
orbital.
more sophisticated MO methods attempt to overcome this difficulty.
The energy of the electron for which the wave functions, + is given by


Mother Nature always builds systems in states of lowest energy.

Energy c calculated from the above equation always will be greater than
Eo, the true minimum energy, unless we have chosen the correct set of
coefficients, c
rj
,
So, if we can find the minimum of the energy with respect to the coefficients,
we must have the right answer for both the energy and the coefficients.
The molecular wave function can be written as the linear combination of the two
carbon 2p atomic wave functions:


Substituting the right side of this expression into the Schroedinger equation
Multiply through
Extract the coefficients from the integrals (which we can do because they're
constants)





Integrals of the type |
i
H |
j
will be replaced by H
ij
Integrals of the type |
i
|
j
will be replaced by S
ij
.

With these substitutions the energy expression becomes:



To make differentiation easier, multiply through by the denominator:



Now take the partial derivative with respect to c
1
, leading to:




Apply the variation principle and set dc/c
1
= 0, and we obtain:


which can be rearranged to


Likewise, partial differentiation with respect to c
2
leads to


This is a completely general result: taking a linear combination of n AOs of any
kind (s, p, d....) leads to a set of n simultaneous equations:






Now, we make a set of additional assumptions to reduce the complexity of the
linear equations.
1. The integrals of type H
ij
, where i = j, are related to the energy of an electron in
an isolated carbon 2p orbital. They are called Coulomb integrals.
We assume they all are equal, regardless of the molecular environment
of the particular carbon
We use for all of them the symbol o.
2. The integrals of the form H
ij
, where I j, are related to the energy lowering
that occurs upon allowing an electron to occupy both orbitals.
This energy is dependent upon the distance between the orbitals.
Hckel theory assumes that if i and j are on adjacent atoms, the
interaction will be the same.
These integrals are represented by |; they are the resonance integrals.
If i and j are not adjacent, we assume there is no energy gain, and set
these integrals equal to zero.
3. The S type integrals are called overlap integrals. They are related to the
energy of interaction between electrons in i and j. We assume they can be
divided into two groups.
If i = j, we set the integrals = 1
If i does not equal j, we set them = 0
This trick, of ignoring differences in interaction between orbitals, is
called neglect of differential overlap, or NDO.

We can summarize the assumptions in the form of a table:






Substituting the values into the set of simultaneous equations yields:














This determinant is called the secular equation.

Returning to ethylene, we find that the secular equation comes out to be:


Some facts about the roots of polynomial equations from Secular
determinants:

1. Since no carbon atom in a t-lattice can be bounded to more than 3 other
carbons, no root can equal or exceed three in magnitude; i.e. |x
j
| < 3.

2. The algebraic sum of all roots vanishes; i.e. Ex
j
=0.

3. The hydrocarbons can be classified into Alternant hydrocarbon (AH)
and Non-Alternant hydrocarbon (Non-AH).

4. Alternant hydrocarbons are planar conjugated hydrocarbons having no
odd-membered rings, in which the carbons can be divided into two sets,
s(starred) and u(unstarred), such that each s-carbon has only u-
neighbours and vice versa.

Even AH: no. of s-carbon = no. of u-carbon positions, the roots take
the form of x
j
= x1, x2, x3,




*
*
*
*
In some cases no. of starred positions is larger than no. of unstarred
positions (ns > nu). In such cases (ns-nu) xs = 0.




Odd-AH, The starred set exceeds the unstarred set by one; the
starred carbons are referred to as active positions. For these systems,
the roots also occurs in pairs and extra root has the value zero.

*
*
*
*
1
2
3
4
5
6
7
8
9
10
1.173
1.173
1.047
0.855
0.986
0.870
0.855
0.986
1.027
1.027
Nucleophilic
Substitution
Electrophilic
Substitution

Atom
Bond Type - electrons
for atom
h
X
k
XY

C
-C=C-
1 0 1.0
N
-C=N-(Pyridine)
1 0.5 1.0
N
=C-N<(Pyrrole)
2 1.5 0.8
N
-N=N-(Azo)
1 1.0 1.0
O
-C=O (carbonyl)
1 1.0 1.0
O
=C-O- (furan)
2 2.0 0.8
F
=C-F
2 3.0 0.7
Cl
=C-Cl
2 2.0 0.4
Br
=C-Br
2 1.5 0.3
S
=C-S- (thiophene)
2 1.5 0.8
FRMALDEHYDE:


a =
0. 1.
1. 1.



H
2
C O

Energy() 0.618034 -1.618034 -electron density
Atom No. Coefficients
1 -0.851 0.526 0.553
2 0.526 0.851 1.447
METHYLIMINE:





0. 1.
1. 0.5
H
2
C NH

Energy() 0.781 -1.281 -electron density
Atom No. Coefficients
1 -0.788 0.615 0.757
2 0.615 0.788 1.243
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Problem from Quantum Chemistry I.N. Levine, Chapter 8, page 241,
5
th
Edition
For more extensive description of the method and its applications, the best
sources are two classic texts:

1. Roberts, J. D., "Notes on Molecular Orbital Calculations", W. A. Benjamin,
Menlo Park, CA, 1962

2. Streitwieser, Jr., A., "Molecular Orbital Theory for Organic Chemists", Wiley,
New York, 1961