Pauling actually begins his discussion with the wavefunction for the molecule A­A:

YAA = aYA­A + bYA+ + bYA¯A+

The contribution of bYA+ and bYA¯A+ to the overall bond energy would be small. Without saying so, Pauling goes on to ignore this portion of the wavefunction.

This leaves: YAA = aYA­A

A similiar wavefunction can be written for the molecule B­B.

Here is what he then says:

Now let us consider a molecule A­B, involving a single bond between two unlike atoms. If the atoms were closely similar in character, the bond in this molecule could be represented by a wave function such as 3-1 [the first one above], an average of those for the symmetric molecules A­A and B­B. Let us describe such a bond as a normal covalent bond. (p. 80, italics his)

The key point is that the wave function for A­B can be considered as an average of those for A­A and B­B.

So, if you knew the value for YAA and for YBB, you could average those two values to get one for aYA­B.

Now, be real careful. That last value is on the right-hand side (the first value) of the wavefunction at the top of the file you came from. (I've put it just below also.) IT IS NOT YAB. This is an experimentally determined value.

Let's do that again because it's important. Here the wavefunction for AB:

YAB = aYA­B + bYA+ + dYA¯B+

The "normal covalent bond" is the part I've put in boldface. It is obtained by averaging two experimental values (YAA and YBB). The actual value for the bond energy is YAB, which is only obtained by experiment.

Pauling will discover a difference in the values for YAB and YA­B. From that difference, he will draw the meaning of electronegativity.


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