Auxiliary-field quantum Monte Carlo calculations of molecular systems with a Gaussian basis

Details Auxiliary-field quantum Monte Carlo calculations of molecular systems with a Gaussian basis Auxiliary-field quantum Monte Carlo calculations of molecular systems with a Gaussian basis

2006-03-07

arxiv.org/abs/physics/0603055v2

J. Chem. Phys. 124, 224101 (2006)

Physics

Computational Physics

11 pages, 5 figures. submitted to JCP

Scientific paper

10.1063/1.2200885

We extend the recently introduced phaseless auxiliary-field quantum Monte Carlo (QMC) approach to any single-particle basis, and apply it to molecular systems with Gaussian basis sets. QMC methods in general scale favorably with system size, as a low power. A QMC approach with auxiliary fields in principle allows an exact solution of the Schrodinger equation in the chosen basis. However, the well-known sign/phase problem causes the statistical noise to increase exponentially. The phaseless method controls this problem by constraining the paths in the auxiliary-field path integrals with an approximate phase condition that depends on a trial wave function. In the present calculations, the trial wave function is a single Slater determinant from a Hartree-Fock calculation. The calculated all-electron total energies show typical systematic errors of no more than a few milli-Hartrees compared to exact results. At equilibrium geometries in the molecules we studied, this accuracy is roughly comparable to that of coupled-cluster with single and double excitations and with non-iterative triples, CCSD(T). For stretched bonds in H$_2$O, our method exhibits better overall accuracy and a more uniform behavior than CCSD(T).

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