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/content/aip/journal/jcp/144/15/10.1063/1.4947093
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/content/aip/journal/jcp/144/15/10.1063/1.4947093
2016-04-20
2016-12-11

Abstract

All-electron Fixed-node DiffusionMonte Carlo calculations for the nonrelativistic ground-state energy of the water molecule at equilibrium geometry are presented. The determinantal part of the trial wavefunction is obtained from a selected Configuration Interaction calculation[Configuration Interaction using a Perturbative Selection done Iteratively (CIPSI) method] including up to about 1.4 × 106 of determinants. Calculations are made using the cc-pCVZ family of basis sets, with = 2 to 5. In contrast with most quantum Monte Carlo works no re-optimization of the determinantal part in presence of a Jastrow is performed. For the largest cc-pCV5Z basis set the lowest upper bound for the ground-state energy reported so far of −76.437 44(18) is obtained. The fixed-node energy is found to decrease regularly as a function of the cardinal number and the Complete Basis Set limit associated with is easily extracted. The resulting energy of −76.438 94(12) — in perfect agreement with the best experimentally derived value — is the most accurate theoretical estimate reported so far. We emphasize that employing selected configuration interactionnodes of increasing quality in a given family of basis sets may represent a simple, deterministic, reproducible, and systematic way of controlling the fixed-node error in diffusionMonte Carlo.

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