The origin of deficiency of the supermolecule second-order Mo\ller-Plesset approach for evaluating interaction energies

Cybulski, Slawomir M.; Lytle, Marion L.
October 2007
Journal of Chemical Physics;10/14/2007, Vol. 127 Issue 14, p141102
Academic Journal
Calculations for the complex of thymine and adenine are used to show that the supermolecule second-order Mo\ller-Plesset perturbation theory (MP2) approach for evaluating interaction energies fails in certain cases because of the behavior of one of its components: the uncoupled Hartree-Fock dispersion energy. A simple approach for correcting the MP2 supermolecule interaction energies is proposed. It focuses on correcting a relatively small difference between the MP2 and coupled cluster interaction energies, which is a very appealing feature of the new approach considering a benchmark role played by coupled cluster results.


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