TY - JOUR
T1 - Accurate, efficient, and simple forces computed with quantum Monte Carlo methods
AU - Chiesa, Simone
AU - Ceperley, D. M.
AU - Zhang, Shiwei
N1 - Copyright:
Copyright 2009 Elsevier B.V., All rights reserved.
PY - 2005/1/28
Y1 - 2005/1/28
N2 - Computation of ionic forces using quantum Monte Carlo methods has long been a challenge. We introduce a simple procedure, based on known properties of physical electronic densities, to make the variance of the Hellmann-Feynman estimator finite. We obtain very accurate geometries for the molecules H 2, LiH, CH4, NH3, H2O, and HF, with a Slater-Jastrow trial wave function. Harmonic frequencies for diatomics are also in good agreement with experiment. An antithetical sampling method is also discussed for additional reduction of the variance.
AB - Computation of ionic forces using quantum Monte Carlo methods has long been a challenge. We introduce a simple procedure, based on known properties of physical electronic densities, to make the variance of the Hellmann-Feynman estimator finite. We obtain very accurate geometries for the molecules H 2, LiH, CH4, NH3, H2O, and HF, with a Slater-Jastrow trial wave function. Harmonic frequencies for diatomics are also in good agreement with experiment. An antithetical sampling method is also discussed for additional reduction of the variance.
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U2 - 10.1103/PhysRevLett.94.036404
DO - 10.1103/PhysRevLett.94.036404
M3 - Article
C2 - 15698293
AN - SCOPUS:18044384242
SN - 0031-9007
VL - 94
JO - Physical review letters
JF - Physical review letters
IS - 3
M1 - 036404
ER -