Issue 43, 2008

Second-order exchange-induction energy of intermolecular interactions from coupled cluster density matrices and their cumulants

Abstract

A new formulation of the second-order exchange-induction energy of symmetry-adapted perturbation theory is presented. In the proposed formalism the exchange-induction energy is expressed through one- and two-particle reduced density matrices of monomers, which are of zeroth and first order with respect to the effective electrostatic potential of another monomer. The resulting expression is further modified by using the partition of two-particle density matrices into the antisymmetrized product of one-particle density matrices and the remaining cumulant part. The proposed formalism has been applied to the case of closed-shell monomers and for density matrices obtained from the expectation-value expression with coupled cluster singles and doubles wave functions. The performance of the new approach has been demonstrated on several benchmark van der Waals systems, including dimers of argon, water, and ethyne.

Graphical abstract: Second-order exchange-induction energy of intermolecular interactions from coupled cluster density matrices and their cumulants

Article information

Article type
Paper
Submitted
30 Apr 2008
Accepted
25 Jul 2008
First published
26 Sep 2008

Phys. Chem. Chem. Phys., 2008,10, 6509-6519

Second-order exchange-induction energy of intermolecular interactions from coupled cluster density matrices and their cumulants

T. Korona, Phys. Chem. Chem. Phys., 2008, 10, 6509 DOI: 10.1039/B807329E

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