Extrapolation and perturbation schemes for accelerating the convergence of quantum mechanical free energy calculations via the Fourier path-integral Monte Carlo method

Steven L. Mielke, Jay Srinivasan, Donald G. Truhlar

Research output: Contribution to journalArticlepeer-review

31 Scopus citations

Abstract

We present two simple but effective techniques designed to improve the rate of convergence of the Fourier path-integral Monte Carlo method for quantum partition functions with respect to the Fourier space expansion length, K, especially at low temperatures. The first method treats the high Fourier components as a perturbation, and the second method involves an extrapolation of the partition function (or perturbative correction to the partition function) with respect to the parameter K. We perform a sequence of calculations at several values of K such that the statistical errors for the set of results are correlated, and this permits extremely accurate extrapolations. We demonstrate the high accuracy and efficiency of these new approaches by computing partition functions for H2O from 296 to 4000 K and comparing to the accurate results of Partridge and Schwenke.

Original languageEnglish (US)
Pages (from-to)8758-8764
Number of pages7
JournalJournal of Chemical Physics
Volume112
Issue number20
DOIs
StatePublished - May 22 2000

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