Molecular Applications of Coupled Cluster and Many-Body Perturbation Methods

Abstract

A series of molecular applications of many-body perturbation theory (MBPT) and the coupled-cluster doubles (CCD) model are described. Even though these methods have been available for sometime, only recently have large scale, MBPT molecular calculations become available. In the case of CCD, the results presented here are among the first obtained from a general purpose ab initio program. The intention of this paper is to present an overview of the current state of the many-body approach to ground state properties of molecules. The properties studied are correlation energies, including contributions from single, double, and quadruple excitations diagrams in fourth-and higher-order; dissociation energies; potential energy surfaces; and molecular polarizabilities and hyperpolarizabilities. Examples are taken from studies of a variety of molecules including HF, H2O, HCO, C6H6, B2H6, CO2, and N2. In many cases, it is found that quantitatively accurate dissociation energies, geometries, and force constants can be obtained. In an illustration of the X1Σg+ potential energy curve of N2, it is shown that a single UHF or RHF reference function MBPT/CCD approach is inadequate at some internuclear separation.

Keywords

Affiliated Institutions

• Battelle US

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