Effects of Electron Correlation upon Molecular Interactions. Correction of the Electrostatic Interaction between DNA Bases

Document Type

Article

Journal/Book Title

Journal of Molecular Structure: TheoChem

Publication Date

10-1988

Publisher

Elsevier

Volume

179

Issue

1

First Page

177

Last Page

184

Abstract

A procedure is advanced for correcting the electrostatic portion of the interaction energy for the effects of intramolecular electron correlation. This expression, which specifically treats the dipole-dipole term, involves the interaction between the Hartree-Fock dipole moment of one subunit and the second-order perturbation correction of its partner (plus the converse). The algorithm is tested on 28 different DNA base pairs, whose interaction energies have been evaluated previously as a sum of the (superposition-corrected) SCF interaction plus the (London) dispersion energy. While the correlation correction is negligible for certain pairs, it is quite sizable in others, in one case lowering the long-range dipole-dipole interaction energy by 27%. On the other hand, the poor convergence of the multipole expansion at equilibrium separation leads to unsatisfactory results at this geometry. It is suggested that a distributed multipole approach would yield superior results over a wide range of intermolecular distance.

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http://www.sciencedirect.com/science/article/pii/0166128088801222

Publisher PDF is available for download through the link above.

Published by Elsevier in Journal of Molecular Structure.

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