Exercise 14 - Calculating Pi-Electrons Charge

Theoretical Organic Chemistry, 2013

Anastazija Ristovska

The -electron charge of the atom is given by

2
=
=1

where is the number of electrons in a particular and is the coefficient of participation of the atom
in that particular .
4
3
2
1

Atom 1 (O) Atom 2 (C2)

0.177
-0.551
0.396
-0.618
0.662
0.000
0.611
0.561

Atom 3 (C3)
0.677
-0.164
-0.530
0.484

Atom 4 (C4)
-0.455
0.659
-0.530
0.279

The calculations for acrolein are as follows:

Atom 1: = 2[(0.611)2+(0.662)2] 0[(0.396)2+(0.177)2]= 1.623

Atom 2: 2
= 2[(0.561)2+(0.000)2] 0[(-0.618)2+(-0.551)2]= 0.629

Atom 3: 3
= 2[(0.484)2+(-0.530)2] 0[(-0.164)2+(0.677)2]= 1.030

Atom 4: 4
= 2[(0.279)2+(-0.530)2] 0[(0.659)2+(-0.455)2]= 0.717

The pure charge of atom , defined as the formal charge which is 1 for all atoms in acrolein minus the
-electrons charge, is given in the table below:
Atom r
1
2
3
4

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

1.623
0.629
1.030
0.717

Atom 1
0.000
0.000
0.000
0.000
1.000
0.000
0.000

-0.623
0.371
-0.030
0.283

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

Atom 1: = 2[(0.000)2+(0.000)2+(1.000)2+(0.000)2]

0[(0.000)2+(0.000)2+(0.000)2]

= 2.000

Atom 2: 2
= 2[(0.232)2+(0.418)2+(0.000)2+(-0.521)2] 0[(0.521)2+(0.418)2+(0.232)2]

= 1.000

Atom 3: 3
= 2[(0.418)2+(0.521)2+(0.000)2+(-0.232)2] 0[(-0.232)2+(-0.521)2+(-0.418)2] = 1.000

Atom 4: 4
= 2[(0.521)2+(0.232)2+(0.000)2+(0.418)2] 0[(-0.418)2+(0.232)2+(0.521)2] = 1.000

Atom 5: 5
= 2[(0.521)2+(-0.232)2+(0.000)2+(0.418)2] 0[(0.418)2+(0.232)2+(-0.521)2] = 1.000

Atom 6: 6
= 2[(0.418)2+(-0.521)2+(0.000)2+(-0.232)2] 0[(0.232)2+(-0.521)2+(0.418)2] = 1.000

Atom 7: 7
= 2[(0.232)2+(-0.418)2+(0.000)2+(-0.521)2] 0[(-0.521)2+(0.418)2+(-0.232)2] = 1.000

Atom r
1
2
3
4
5
6
7

2.000
1.000
1.000
1.000
1.000
1.000
1.000

-1.000
0.000
0.000
0.000
0.000
0.000
0.000

The pure charge of each atom in 2-ethenylpyrrole is given in the table above.

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.