64 Ch.

2 Atoms, Ions, and Molecules

2.5.3 Molecular Orbitals versus Heitler-London

The role of the ionized configurations is increasing if the interatomic
distance IR, - Rb(is reduced, because t becomes larger. At sufficiently
small /R,- Rb] we may argue that the single-electron hopping is the
dominating effect and electron-electron interaction can be treated as a
perturbation. This scenario also leads to a singlet ground state.
In this molecular orbital treatment, we start with the single-electron
eigenstates of the molecule: these are the even, and odd, molecular
orbitals:

(2.139)

The corresponding single-electron energies are

(2.140)

Obviously, we are doing best by putting both electrons into the even
(bonding) state, and leaving the odd (antibonding) state empty

(2.141)

This is the prescription of the molecular orbital method for the ground
state. We recognize that this is band theory applied to the H2 molecule.
We solved the one-electron problem, and filled the energy levels from
bottom upwards.
Where remain all the problems with the electron-electron interac-
tion? We will spot them immediately if we expand the molecular orbital
(MO) ground state

(2.142)