## 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 k_{B}T, 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 language | English (US) |
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Pages (from-to) | 445-453 |

Number of pages | 9 |

Journal | Chemical Physics Letters |

Volume | 351 |

Issue number | 5-6 |

DOIs | |

State | Published - Jan 17 2002 |

Externally published | Yes |

## ASJC Scopus subject areas

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