TY - JOUR

T1 - Overcoming finite-sampling errors in fast-switching free-energy estimates

T2 - Extrapolative analysis of a molecular system

AU - Zuckerman, Daniel M.

AU - Woolf, Thomas B.

N1 - Funding Information:
Many people provided helpful comments and suggestions for the research reported here. The authors would like to thank Lucy Forrest, Lancelot James, Chris Jarzynski, Hirsh Nanda, Horia Petrache, Lawrence Pratt, Mark Robbins, Jonathan Sachs, Thomas Simonson, Attila Szabo, Scott Zeger, and David Zuckerman. Special thanks are due to David Hendrix and Chris Jarzynski for permission to use the raw data produced for [11] . Funding for this work was provided by the NIH (Grant GM54782), the Bard Foundation, and the Department of Physiology. D.M.Z. is the recipient of a National Research Service Award (GM20394) from the NIH.

PY - 2002/1/17

Y1 - 2002/1/17

N2 - 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.

AB - 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.

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U2 - 10.1016/S0009-2614(01)01397-5

DO - 10.1016/S0009-2614(01)01397-5

M3 - Article

AN - SCOPUS:0037122460

VL - 351

SP - 445

EP - 453

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

IS - 5-6

ER -