### 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) |
---|---|

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 |

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### 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.

Research output: Contribution to journal › Article

*Chemical Physics Letters*, vol. 351, no. 5-6, pp. 445-453. https://doi.org/10.1016/S0009-2614(01)01397-5

}

TY - JOUR

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

T2 - Extrapolative analysis of a molecular system

AU - Zuckerman, Daniel

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.

UR - http://www.scopus.com/inward/record.url?scp=0037122460&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0037122460&partnerID=8YFLogxK

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

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

M3 - Article

VL - 351

SP - 445

EP - 453

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

IS - 5-6

ER -