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Molecular physics and chemistry applications of quantum Monte Carlo

Journal Article · · J. Stat. Phys.; (United States)
DOI:https://doi.org/10.1007/BF02628327· OSTI ID:5428358

We discuss recent work with the diffusion quantum Monte Carlo (QMC) method in its application to molecular systems. The formal correspondence of the imaginary-time Schroedinger equation to a diffusion equation allows one to calculate quantum mechanical expectation values as Monte Carlo averages over an ensemble of random walks. We report work on atomic and molecular total energies, as well as properties including electron affinities, binding energies, reaction barriers, and moments of the electronic charge distribution. A brief discussion is given on how standard QMC must be modified for calculating properties. Calculated energies and properties are presented for a number of molecular systems, including He, F, F/sup -/, H/sub 2/, N, and N/sub 2/. Recent progress in extending the basic QMC approach to the calculation of ''analytic'' (as opposed to finite-difference) derivatives of the energy is presented, together with an H/sub 2/ potential-energy curve obtained using analytic derivatives.

Research Organization:
Materials and Molecular Research Division, Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
DOE Contract Number:
AC03-76SF00098
OSTI ID:
5428358
Journal Information:
J. Stat. Phys.; (United States), Journal Name: J. Stat. Phys.; (United States) Vol. 43:3; ISSN JSTPB
Country of Publication:
United States
Language:
English