Exercise 11: Heteroatoms in the HMO Method

Theoretical Organic Chemistry, 2013

Anastazija Ristovska
H2C=CH-CH=CH2 butadiene
H2C=CH-CH=O acrolein (propenal)
In order to be able to use the Huckel method on conjugated systems with heteroatoms it is necessary that
corrections are introduced, such as the inclusion of coulomb and resonance integrals for heteroatoms
(different than those for carbon) in the secondary equations.
=

Coulomb integral

Resonance integral

= +

The formula used to derive the Coulomb integral from the and values for
carbon atoms. The values are given in literature. Carbon is taken to be
the reference atom for the parameter, and the values for
heteroatoms are either smaller or larger than .

The formula used to derive the Resonance integral from the value
for carbon atoms. The values are given in literature.

Acrolein Calculations
Etot=4+5,81

Using the given values for and 1, we create the characteristic determinant of acrolein.
1
2
3
4

The values were found using the 64-bit Java applet HuLiS 3.0 JDK 1.7.0_45. (c) Copyright HuLiS
contributors 2007. All rights reserved.

1
2
3
4

2
1

1,06

1,06
+ 0,97

It is alright to display it as follows, for simplicity:

1
2
3
4

2
1

1,06

1,06
0.97

The values that are imputed into the Huckel program are
the following:
1
2
3
4

1
0
1

Orbital
MO 4
MO 3
MO 2
MO 1
total energy

2
1
0
1

1
0
1,06

1,06
0.97

Energy (B)
Electrons
-1,550
0
-0,383
0
0,991
2
1,912
2
8,988

The graphs below depict the electron density distribution per atom for each of acrolein.

Constructing the characteristic determinant for 2-Ethenylpyrrole

Figure 1: 2-Ethenylpyrrole HMO Energies Diagram

Characteristic Determinant:
1
2
3
4
5
6
7

1
1,37
0,89

2
0,89
0
1

3
1
0
1

0,89

4
1
0
1

5
0,89
1
0
1

1
0
1

1
0

These parameters are different in various sources, and in the above table it is seen how the HuLiS
software displayed different values than the Huckel-H software:
Atom
1
2
3
4
5
6
7

1
1,5
0,8

0,8

2
0,8
0,0
1,0

3
1,0
0,0
1,0

1,0
0,0
1,0

5
0,8

1,0
0,0
1,0

1,0
0,0
1,0

1,0
0,0

The graphs below depict the electron density distribution per atom for each of 2-ethenylpyrrole.

All calculations were conducted using the 32-bit Huckel Molecular Orbitals (HMO) Calculations
Software, Copyright 1993 by David R. Anderson, Department of Chemistry, University of Colorado,
Colorado Springs, CO 80933; and the 64-bit Java applet HuLiS 3.0 JDK 1.7.0_45, (c) Copyright HuLiS
contributors 2007: Nicolas Goudard, Yannick Carissan, Denis Hagebaum-Reignier et Stphane Humbel,
Campus St. Jrme, Av. Escadrille Normandie-Niemen, 13397 Marseille Cedex 20 France. All rights
reserved. The program was created based on the following publications:
Y. Carissan, D. Hagebaum-Reignier, N. Goudard, S. Humbel Hckel-Lewis-Projection Method: A Weights
Watcher for Mesomeric Structures: J. Phys. Chem. A. 2008, 112 (50), 1325613262
D. Hagebaum-Reignier, R. Girardi, Y. Carissan, S. Humbel Hckel theory for Lewis structures J. Mol.
Struct. (THEOCHEM) 2007, 817 99-109
S. Humbel Getting the Weights of Lewis Structures out of Hckel Theory: HckelLewis Configuration Interaction J.
Chem. Educ. 2007 84 , 1056-1061