Quantum Mechanics of the H2–H2 Interaction. V. The Importance of Intermolecular Charge-Transfer States

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Abstract
In a preceding paper a one‐configuration wavefunction of strong orthogonal group functions was found to give a rather poor description of the orientation dependence of short‐range intermolecular forces in H2–H2. As an alternative to the necessity of relaxing the strong orthogonality condition, it is suggested that the introduction of a small amount of the charge‐transfer state H2−–H2+ describing one‐electron transfer between the two molecules should improve the interaction energy and its change with the relative molecular orientation. Ab initio calculations in a region of intermolecular separations ranging from two to four times the internuclear equilibrium distance of an isolated H2 molecule show that less than 1% of such a charge‐transfer state gives interaction energies which are in substantial agreement with those obtained with a complete configurational interaction.

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