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Valence energy in variational Monte Carlo: CuH dissociation energy
Author(s) -
Rothstein Stuart M.
Publication year - 1996
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1996)60:4<803::aid-qua2>3.0.co;2-0
Subject(s) - dissociation (chemistry) , monte carlo method , pseudopotential , valence (chemistry) , chemistry , diffusion monte carlo , dipole , atomic physics , statistical physics , physics , hybrid monte carlo , quantum mechanics , markov chain monte carlo , mathematics , statistics
We show how to estimate the dissociation energy of CuH using the variational Monte Carlo method. The techniques involved are (i) an all‐electron approach, (ii) a diffusion‐only Metroplis algorithm which is well‐suited for sampling the nodal regions properly, and (iii) a core‐valence partitioning scheme such that the dissociation energy is estimated from the valence energies of CuH and Cu only. This approach avoids several of the approximations inherent in pseudopotential methods. Using relatively crude wave functions, we obtain an estimate of the dissociation energy and dipole moment with an accuracy on par with much more elaborate calculations in the literature. © 1996 John Wiley & Sons, Inc.