Overcoming finite-sampling errors in fast-switching free-energy estimates

Extrapolative analysis of a molecular system

Daniel Zuckerman, Thomas B. Woolf

Research output: Contribution to journalArticle

57 Citations (Scopus)

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
Externally publishedYes

Fingerprint

Free energy
sampling
free energy
Sampling
Extrapolation
extrapolation
estimates
Ethane
ethane
Methanol
switches
methyl alcohol
Switches

ASJC Scopus subject areas

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

Cite this

Overcoming finite-sampling errors in fast-switching free-energy estimates : Extrapolative analysis of a molecular system. / Zuckerman, Daniel; Woolf, Thomas B.

In: Chemical Physics Letters, Vol. 351, No. 5-6, 17.01.2002, p. 445-453.

Research output: Contribution to journalArticle

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