Using perturbatively selected configuration interaction in quantum Monte Carlo calculations

ISSN： 1480-3291

Source： Canadian Journal of Chemistry, Vol.91, Iss.9, 2013-01, pp. : 879-885

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Abstract

Defining accurate and compact trial wavefunctions leading to small statistical and fixed-node errors in quantum Monte Carlo (QMC) calculations is still a challenging problem. Here we propose to make use of selected configuration interaction (CI) expansions obtained by selecting the most important determinants through a perturbative criterion. A major advantage with respect to truncated CASSCF wavefunctions or CI expansions limited to a maximum number of excitations (e.g, CISD) is that much smaller expansions can be considered (many unessential determinants are avoided), an important practical point for efficient QMC calculations. The most important determinants entering first during the selection process (hierarchical construction) the main features of the nodal structure of the wavefunction can be expected to be obtained with a moderate number of determinants. Thanks to this property, the delicate problem of optimizing in a Monte Carlo framework the numerous linear and (or) nonlinear parameters of the determinantal part of the trial wavefunction could be avoided. As a first numerical example, the calculation of the ground-state energy of the oxygen atom is presented. The best DMC value reported so far is obtained.