Overcoming finite-sampling errors in fast-switching free-energy estimates: Extrapolative analysis of a molecular system

Daniel M. Zuckerman, Thomas B. Woolf

Research output: Contribution to journalArticle

57 Scopus citations

Abstract

We perform a block-averaging and extrapolation analysis of fast-switching free-energy difference (ΔF) estimates for a computer-modeled, fully solvated ethane ↔ methanol transformation. The results suggest that the analysis can greatly reduce the 'finite-sampling error' in ΔF estimated from a small number of very fast switches. This error, which can be many times kBT, is the difference between an estimate based on a finite amount of data and that from an infinite data set; it is inherent in the ΔF calculations. Our blocking/extrapolation procedure appears to be particularly useful for broad, non-Gaussian distributions of data which typically produce large finite-sampling errors.

Original languageEnglish (US)
Pages (from-to)445-453
Number of pages9
JournalChemical Physics Letters
Volume351
Issue number5-6
DOIs
StatePublished - Jan 17 2002

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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