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.

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 -