Exercise 13: HMO Calculations for Heteroatomic Molecules

Theoretical Organic Chemistry, 2013

Anastazija Ristovska
2-Ethenylpyrrole

Figure 1: 2-Ethenylpyrrole Structural Formula

2-Ethenylpyrrole belongs to the class of azole compounds which are cyclic rings of five members, one or
two of which are nitrogen (e.g. pyrrole, pyrazole, imidazole) and the rest are carbon, or, one of which is
nitrogen, one is oxygen (e.g. oxazole, isoxazole) or sulfur (thiazole), and the other three are carbon atoms.
This molecule has 7 atoms, but 8 -electrons because, apart from the 6 electrons from the double bonds
visible in the molecular structure, there is also a free electron pair on the nitrogen atom that participates
in the -electron conjugated chain.
Orbital
MO 7
MO 6
MO 5
MO 4
MO 3
MO 2
MO 1
total energy

Energy (B)
Electrons
-1,802
0
-1,247
0
-0,455
0
0,455
2
1
2
1,247
2
1,802
2
8,988

Table 1: 2-Ethenylpyrrole beta pi energies

Atom

1,5

0,8

0,8

0,0

1,0

1,0

0,0

1,0

1,0

0,0

1,0

1,0

0,0

1,0

1,0

0,0

1,0

1,0

0,0

3
4
5

0,8

0,8

6
7
Table 2: 2-Ethenylpyrrole Huckel Matrix

The 0,0 values along the diagonal mean that atoms 2, 3, 4, 5, 6, and 7 are carbon atoms, whereas the 1.5
value in the first diagonal field indicates that the first atom is a nitrogen with one free electron pair. The
values 1.0 for the bonds between atoms 2&3, 3&4, 4&5, 5&6, and 6&7 indicate that these bonds are
carbon-carbon bonds, whereas the value of 0.8 for the bonds between atomic pairs 1&2 and 1&5
indicates these are C-N bonds with a partial conjugated double-bond character.
The densities of all atoms are unity (1.000)whereas at the nitrogen atom the electron density is 2.000.

Figure 2: 2-Ethenylpyrrole HMO Energies Diagram

Figure 3: 2-Ethenylpyrrole HMO Energies HOMO LUMO Diagram

Atom Pair
C3-C2
C7-C6
C5-C4
C4-C3
C6-C5
N-C2
N-C5

Bond Order
0.871
0.871
0.785
0.483
0.483
0.000 ?
0.000 ?

Type of Bond
Double
Double
Double
Single
Single
?? - conjugated
?? - conjugated

Table 3: 2-Ethenylpyrrole Bond Order Table

MO 7
MO 6
MO 5
MO 4
MO 3
MO 2
MO 1

Atom 1
0.000
0.000
0.000
0.000
1.000
0.000
0.000

Atom 2
0.232
0.418
0.521
-0.521
0.000
0.418
0.232

Atom 3
-0.418
-0.521
-0.232
-0.232
0.000
0.521
0.418

Atom 4
0.521
0.232
-0.418
0.418
0.000
0.232
0.521

Atom 5
-0.521
0.232
0.418
0.418
0.000
-0.232
0.521

Atom 6
0.418
-0.521
0.232
-0.232
0.000
-0.521
0.418

Atom 7
-0.232
0.418
-0.521
-0.521
0.000
-0.418
0.232

Table 4: 2-Ethenylpyrrole MO-Atom Coefficients Table

Pyridine
3

Figure 1: Pyridine Structural Formula

Pyridine has 6 centers (5 carbon and 1 nitrogen atoms), and 6 -electrons. There is one non-bonded
electron on the nitrogen, however it is found in a p-orbital perpendicular to the p-orbital that participates
in the double bond conjugation of the -electron ring. It has 6 molecular orbitals, three of which are
bonding and three of which are anti-bonding. Their energies are displayed in this table:
Orbital
MO 6
MO 5
MO 4
MO 3
MO 2
MO 1
Total Energy

Energy (B)
-1.802
-1.247
-0.445
0.445
1.247
1.802
6.988

Electrons
0
0
0
2
2
2

Table 1: Pyridine MO beta pi Energies

Atom

0,5

0,8

0,8

0,0

1,0

1,0

0,0

1,0

1,0

0,0

1,0

1,0

0,0

1,0

1,0

0,0

3
4
5
6

6
1,0

1,0

Table 2 Pyridine Huckel Matrix

The 0,0 values along the diagonal mean that atoms 2, 3, 4, 5, and 6 are carbon atoms, whereas the 0.5
value in the first diagonal field indicates that the first atom is a nitrogen with one non-bonded electron.
The values 1.0 for the bonds between atoms 2&3, 3&4, 4&5, and 5&6 indicate that these bonds are
carbon-carbon bonds, or a nitrogen-carbon single bond, whereas the value of 0.8 for the bond between
the first and second atom indicates it has a double-bond character.
The densities of all atoms are unity (1.000).

The bond order between atomic pairs N & C6, and C2 & C3, is 0.871, indicating double-bond character;
the bond order between C5 & C6 is 0.483, indicating a single-bond character, whereas the bond order
between C4 & C5 is 0,785, again indicating a double-bond character. However, the bond order table gives
a bond order of 0.000 for the bond between N and C1, indicating that we are missing data that describes
the resonance character of the molecules, i.e. that the double-bond character is placed both on bonds NC1 as well as N-C6. We will later compare these values for that of benzene. The current model used for
our analysis is good for figuring out the energies of the molecular orbitals since if we choose to treat the
pyridine molecule same as benzene in assigning the types of bonds when building the Huckel matrix we
would end up with one electron in an anti-bonding orbital. However, that configuration display, even
though not useful for finding the molecular orbital energies, it is useful for determining the bond orders
accurately.
Atom 1
Atom 2
Atom 3
Atom 4
Atom 5
Atom 6

Atom 1
0
0
0
0
0
0.871 ||

Atom
0
0
0.871 ||
0
0
0

Atom 3
0
0.871 ||
0
0.483 |
0
0

Atom 4
0
0
0.483 |
0
0.785 ||
0

Atom 5
0
0
0
0.785 ||
0
0.483 |

Atom 6
0.871 ||*
0
0
0
0.483 |
0

Table 3: Pyridine Bond Orders

*|| = double bond, | = single bond

MO 7
MO 6
MO 5
MO 4
MO 3
MO 2

Atom 1
0.232
0.418
0.521
0.521
0.418
0.232

Atom
-0.232
0.418
-0.521
0.521
-0.418
0.232

Atom 3
0.418
-0.521
0.232
0.232
-0.521
0.418

Atom 4
-0.521
0.232
-0.418
-0.418
-0.232
0.521

Atom 5
0.521
0.232
-0.418
-0.418
0.232
0.521

Atom 6
-0.418
-0.521
-0.232
0.232
0.521
0.418

Table 4: Pyridine Coefficients

2-Ethenylpyrrole: Adjusted Calculations

Figure 1: 2-Ethenylpyrrole

When we use different settings for assigning the character of the bonds in 1-ethenylpyrrole we obtain
different energy values and different coefficients. If we prefer to treat the character of both C-N bonds as
we treat the nature of the C-C bonds in a benzene molecule, then it is hard to decide which C-N bond is a
double bond, and which one is a single bond. It is therefore necessary to choose single bond settings for
both C-N bonds and allow the program to assess the bond character more precisely by analyzing the
number of electrons and bonding patterns of the entire molecule. In such a case, the total energy is
10.722. The electron densities at each atom are given in the table below, where it can be noticed that
Atom 1, which is nitrogen, has an electron density of 1.733, or almost 2, indicative of the free electron
pair present at nitrogen, and also perhaps indicative of nitrogens electronegativity and electronwithdrawing characteristics. The carbon atoms bonded to nitrogen, atoms 2 and 6, have electron densities
of 1.009 and 1.000, respectively, which are the lowest electron densities in the table, indicating that the
nitrogen has pulled towards itself some of the electron cloud densities of these two atoms, and has done
so uniformly, withdrawing electron density equally from both carbon atoms it is bonded to.
Atom
1
2
3
4
5
6
7

e-Densities
1.733
1.009
1.098
1.084
1.033
1.000
1.043

Table 1: 2-Ethenylpyrrole
Atomic E-Densities, Adjusted

Atom
1
2
3
4
5
6
7

1
1.5
0.8

2
0.8
0
1

3
1
0
1

0.8

1
0
1

5
0.8

1
0
1

1
0
1

1
0

Table 2: 2-Ethenylpyrrole Huckel Matrix, Adjusted

MO
Energy ()
7
-1.825
6
-1.367
5
-0.669
4
0.441
3
1.162
2
1.351
1
2.407
Total energy 10.772

Electrons
0
0
0
2
2
2
2

Table 3: 2-Ethenylpyrrole
MO beta pi Energies, Adjusted

2,5
2
+1,825

Energy, set at zero, plus

1,5

+1,367

1
0,5

+0,699

0
-0,5
-1
-1,5

-0,441

-1,162
-1,351

-2
-2,5

-2,407

-3
Figure 2: 2-Ethenylpyrrole HMO Energies Diagram, Adjusted

Figure 3: 2-Ethenylpyrrole HMO Energies HOMO LUMO Diagram, Adjusted

MO 7
MO 6
MO 5
MO 4
MO 3
MO 2
MO 1

Atom 1
0.098
0.220
0.276
0.052
0.436
0.445
0.690

Atom 2
0.157
-0.538
-0.426
-0.501
-0.252
0.276
0.338

Atom 3
-0.365
0.560
0.065
-0.262
-0.641
0.017
0.262

Atom 4
0.510
-0.227
0.383
0.385
-0.494
-0.253
0.293

Atom 5
-0.564
-0.249
-0.321
0.432
0.067
-0.359
0.444

Atom 6
0.442
0.392
-0.389
-0.236
0.223
-0.587
0.223

Atom 7
-0.242
-0.287
0.581
-0.536
0.192
-0.435
0.093

Table 4: 2-Ethenylpyrrole MO-Atom Coefficients Table, Adjusted

Atom 1
Atom 2
Atom 3
Atom 4
Atom 5
Atom 6
Atom 7

Atom 1
0
0.440 |
0
0
0.397 |
0
0

Atom 2
0.440 |
0
0.772 ||
0
0
0
0

Atom 3
0
0.772 ||
0
0.577 ||
0
0
0

Atom 4
0
0
0.577 ||
0
0.708 ||
0
0

Atom 5
0.397 |
0
0
0.708 ||
0
0.445 |
0

Atom 6
0
0
0
0
0.445 |
0
0.890 ||

Atom 7
0
0
0
0
0
0.890 ||*
0

Table 5: 2-Ethenylpyrrole Bond Orders, Adjusted

*|| = double bond, | = single bond

If this model is applied, strangely enough, both C-N bonds, i.e. the bonds between atoms 1&2 and 1&5,
have bond orders below 0.5, indicating single bonds. It could be possible that, if we assign the Huckel
program C-N bonds that are indicated as single, the program might assume there are no pi electrons on
the nitrogen atom that belong to the only atomic orbital geometrically positioned so as to be able to
participate in the electrons conjugate system, but rather the non-bonded free pi electron pair of
nitrogen is in an atomic orbital perpendicular to the -electron conjugate system.

All calculations were conducted using the Huckel Molecular Orbitals (HMO) Calculations computer
program, Copyright 1993 by David R. Anderson, Department of Chemistry, University of Colorado,
Colorado Springs, CO 80933.

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