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Exercise 23

HyperChem 8.04 CNDO-2 Calculations. Electron Density and Dipole Moment in Molecules
Theoretical Organic Chemistry, 2013
Anastazija Ristovska

Figure 1: 2-Ethenylpyrrole

Doublet state calculation


The half-electron approximation will be used
Number of electrons = 29
Number of Double Occupied Levels = 14
Number of Single Occupied Levels = 1
Charge on the System = 0
Total Orbitals = 28
Energy=-2898.553172 kcal/mol
Gradient=171.342419
Symmetry=CS
There are a total of 28 molecular orbitals, of which 7 are carbon-carbon bonds molecular orbitals, and 21
are carbon-hydrogen bonds orbitals. The total charge of the molecule is 0. The symmetry of the molecule
is CS. The binding energy is -2898.6 kcal/mol.
All calculations and molecular representations were done using the HyperChem v.8.04 Software.

Figure 2: 2-Ethenylpyrrole HMO Energies HOMO LUMO Diagram

The total energy is -33061,2 kcal/mol or -52.69 a.u.; the isolated atomic energy is -30162,7 kcal/mol; the
electronic energy is -90170,4 kcal/mol; the heat of formation is -1760,2 kcal/mol; the core-core
interaction is 57109,2 kcal/mol; HE energy correction: -51,1 kcal/mol; Gradient: 171,3 kcal/mol/. The
molecular point group is CS.

Figure 3: 2-Ethenylpyrrole Numeration

The carbon atom electron configuration is [He] 2s2 2p2 or 1s2 2s2 2p2, for a total of six electrons, of which
only the four valence electrons participate in forming organic bonds. The nitrogen atom configuration is
[He] 2s2 2p3 or 1s2 2s2 2p3.
There are five valence electrons, of which one participates in forming a bond with C4, one participates in
forming a bond with C3, and one forms a bond with a hydrogen atom. The leftover two electrons are a
free electron pair in a p atomic orbital perpendicular to the plane of the molecule and thus able to
participate in the -electron conjugated ring.
The nitrogen atom is sp2 hybridized. That means two of the p , and , merge with the s atomic
orbitals to form two bonds with two different carbon atoms, with one electron participating in each of
those two bonds. The third bond of the sp2 hybridization is used to form a bond with a hydrogen atom.
The non-hybridized is the one that keeps the free electron pair in it perpendicular to the plane of
the sp2 hybridization and thus allowing it to participate in the -electron conjugation.
All carbon atoms are likewise sp2 hybridized, with two of their three sp2 bonds binding to other carbon
atoms or the nitrogen atom, and the third sp2 bond being formed with a hydrogen atom. The 2 bond
which does not participate in the sp2 hybridization or the bonds, participates in the bond formation,
the bond being the second bond of the double bond formed, as seen in Figure 4.

The atomic orbital electron populations of each atom as numbered in the molecule structural
representation above is:
Nitrogen N (7)Atomic Orbital
Electron Population

2
1.590

2
0.965

2
1.011

2
1.568

Carbon C1 Atomic Orbital


Electron Population

2
1.127

2
0.757

2
0.735

2
1.297

Carbon C2 Atomic Orbital


Electron Population

2
1.232

2
0.793

2
0.561

2
1.330

Carbon C3 Atomic Orbital


Electron Population

2
1.326

2
0.866

2
0.974

2
0.862

Carbon C4 Atomic Orbital


Electron Population

2
0.999

2
0.946

2
0.905

2
0.937

Carbon C5 Atomic Orbital


Electron Population

2
1.180

2
0.965

2
0.924

2
1.047

Carbon C6 Atomic Orbital


Electron Population

2
1.652

2
0.777

2
0.833

2
0.841

Figure 4: Double Bond

The net charges and coordinates in a tri-dimensional coordinate system are given in the table below:

If we sum up all the net charges on each individual atom, the total net charge of the molecule will be
0.000000. The Z number is the atomic number or number of protons, whereas the Mass is just the
molecular weight given in Daltons. The coordinates give the location in space of each atom relative to the
origin of a Cartesian 3D coordinate system. This molecule being planar the z-coordinates are all set at
zero, the origin.
The Dipole moment in each direction, given in Debyes, is shown in this table:
Dipole (Debyes)
Point-Charge
sp2 Hybrid
Sum

x
-1.973
-1.126
-3.100

y
1.576
3.084
4.660

z
0.000
-0.093
-0.093

Total
2.525
3.285
5.597

The total values were calculated using the pythagorian theorem in 3D space.

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