(b) Electronegativity

The charge distribution in bonds is commonly

discussed in terms of the electronegativity,
χ, of the elements involved.

 A   B  0,102 D  A  B    D  A  A   D  B  B 
1/2
1
2

Electronegativities based on this definition are called

Pauling electronegativities.
Robert Mulliken argued an element is likely to be highly
electronegative if it has a high ionization energy (so it will
not release electrons readily) and a high electron
affinity (so it is energetically favorable to acquire electrons).

Mulliken electronegativity scale

 M  12  I  Eea 
 The Mulliken and Pauling scales are approximately
in line with each other.

 P  1,35  1/2
M  1,37

The variation principle

Variation principle:

If an arbitrary wavefunction is used to calculate the energy,

the value calculated is never less than the true energy.
This principle is the basis of all modern molecular
structure calculations . The arbitrary wavefunction is
called the trial wavefunction.

The energy of the trial wavefunction is the expectation

value of the energy operator.

ˆ  d
E
  * H

 * d

value of E is minimum
 E E
0 0
c A cB

The denominator is

2
 * d   c A  c B  d
A B

 c  A d  c  B d  2c c  ABd
2
A
2 2
B
2
A B

 c A2  cB2  2c AcB S
 The numerator is

ˆ  d   c A  c B Hˆ  c A  c B  d
  * H  A B A B

ˆ   c 2 BHBd
 c A2  AHAd ˆ   c c AHBd
ˆ   c c BHAd
ˆ 
B A B A B

 c A2 A  cB2 B  2c AcB 

c  A  c  B  2c AcB 
2 2
E A B

c A  c  2c AcB S
2 2
B
cAαA − cAE + cBβ − cBSE = (αA − E)cA + (β − ES)cB = 0

cAβ − cASE + cBαB − cBE = (β − ES)cA + (αB − E)cB = 0

Illustration 11.2 Using the variation principle (1)
To find the energies E of the bonding and antibonding
orbitals of a homonuclear diatomic molecule set with αA
= αB = α