Improved counterpoise corrections for the a b i n i t i o calculation of hydrogen bonding interactions

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Abstract
Counterpoise ab initio calculations have been carried out for the hydrogen fluoride dimer using 14 different basis sets. A counterpoise calculation evaluates the stability contribution arising from just the mutual basis set enlargement of bringing two species into proximity. Using this stability contribution to correct the total interaction energy does not always improve reliability. Furthermore, counterpoise corrections have been found to be misleadingly small in certain cases, suggesting greater reliability than is warranted. The problem is that the counterpoise correction should be the stability contribution arising from the mutual basis set enlargement in the description of the perturbed rather than the isolated bonding partners. In hydrogen bonding, much of the perturbation is an electrical polarization of charge. Thus, we have found that more useful counterpoise correction values are obtained by employing a perturbing charge field. This charge field is approximately that which would arise from the species that is absent in the counterpoise evaluation.

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