Exercise 26 - HyperChem 8.04 AM1 Calculations. Electron Stability of Molecules.

Aromaticity
Theoretical Organic Chemistry, 2013
Anastazija Ristovska

The neutral molecule in its ground state, with total

charge on the system of 0, and spin multiplicity of 1, has an
energy of its highest occupied molecular orbital (HOMO) of 8.340 eV, and an energy of its lowest unoccupied molecular
orbital (LUMO) of 0.584 eV. The difference between the
energies of the LUMO and HOMO orbitals is
[LUMO] [HOMO] = 0.584 - (-8.340) = 8.924 eV. The total
energy is -24611 kcal/mol. The total energy E of the molecule
determines the structure and stability of the molecule, and it represents the sum of the kinetic energies of
all the particles forming the molecules plus the sum of all the potential energies of all the interactions of
the particles forming the molecule. In particular, it is a sum of the kinetic energies of all nuclei, plus the
sum of the potential energy of all Coulomb interactions between nuclei, plus the sum of the potential
energies of all Coulomb interactions between nuclei and electrons, plus the sum of the potential energies
of all Coulomb interactions between electrons. This definition can be simplified by applying the BornOppenheimer approximation according to which the nuclei are assumed to be stationary, i.e. their kinetic
energies are zero, and they are simply point charges, implying that the potential energy of all Coulomb
interactions between nuclei is in fact Coulomb repulsion between point charges. The rest of the energies
that constitute the total energy is the electronic energy, and is found by solving the Schrdinger equation
of the electrons The electronic energy of ground-state 2-ethenylpyrrole is -103279 kcal/mol. The heat of
formation is 166.47 kcal/mol.

The cation of 2-ethenylpyrrole has a total charge on the

system of +1 and spin multiplicity of 1. Its HOMO energy is 16.213 eV, and its LUMO energy is -10.147 eV. The difference
between the energies of the LUMO and HOMO orbitals is
[LUMO] [HOMO] = -10.147-(-16.213) = 6.066 eV. The total
energy is -21728 kcal/mol. The electronic energy is -73548
kcal/mol. The heat of formation is 795.37 kcal/mol.
The anion of 2-Ethenylpyrrole has a total charge on the
system of -1 and spin multiplicity of 1. Its HOMO energy is
-4.182 eV, and its LUMO energy is -1.424 eV. The difference
between the energies of the LUMO and HOMO orbitals is
[LUMO] [HOMO] = 1.424-(-4.182) = 5.606 eV. The total
energy is -22043 kcal/mol. The electronic energy is -73864
kcal/mol. The heat of formation is 479.52 kcal/mol.
The radical of 2-ethenylpyrrole has a total charge on the
system of 0 and spin multiplicity of 2. Its HOMO energy is -7.345
eV, and its LUMO energy is -3.766 eV. The difference between
the energies of the LUMO and HOMO orbitals is [LUMO]
[HOMO] = -3.766-(-7.345) = 3.579 eV. The total energy is -21977
kcal/mol. The electronic energy is -73797 kcal/mol. The heat of
formation is 545.65 kcal/mol.

Total Charge
Spin Multiplicity
Total Energy (kcal/mol)
Electronic Energy (kcal/mol)
Heat of Formation (kcal/mol)
LUMO Energy (eV)
HOMO Energy (eV)
[LUMO]-[HOMO] Energy
(eV)

0
1
-24611
-103279
166.47
0.584
-8.340

+1
1
-21728
-73548
795.37
-10.147
-16.213

-1
1
-22043
-73864
479.52
-1.424
-4.182

0
2
-21977
-73797
545.65
-3.766
-7.345

8.924

6.066

5.606

3.579

The table of comparison shows that the neutral molecule is most stable: it has the lowest total
energy, significantly lowest electronic energy and heat of formation, as well as the greatest difference
between the energies of its LUMO and HOMO orbitals. The next in stability would be the 2ethenylpyrrole radical. Even though the difference between the energies of the LUMO and HOMO
orbitals of the cation is greater than that of the anion, the anion of 2-ethenylpyrrole has the lowest total
energy, lowest electronic energy, and lowest heat of formation among the excited states of this
compound, and therefore it is the next most stable form of the molecule after its neutral form.

All calculations were conducted using the HyperChem v.8.02 Software Package.
Appendix
HOMO/LUMO Charge 0

HOMO/LUMO Charge +1

HOMO/LUMO Charge -1

HOMO/LUMO Radical