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5 - Generalities

Published online by Cambridge University Press:  13 August 2009

Tom L. Beck
Affiliation:
University of Cincinnati
Michael E. Paulaitis
Affiliation:
The Johns Hopkins University
Lawrence R. Pratt
Affiliation:
Los Alamos National Laboratory
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Summary

The following is a survey of some general and useful relations for evaluating chemical potentials and free energy changes. The number of such relations isn't large, but an overview is warranted here. Evaluations of free energy changes are typically the most basic and convincing validations of molecular simulation research. Calculations of free energy changes are typically more specialized undertakings than unspecialized simulations. If the problem at hand has been well-considered and calculations are to be specially directed to evaluate free energy changes, then thermodynamic or coupling parameter integration procedures are likely to be the most efficient possibilities. They are favorably stratified, they can have low bias, it is clear how computational effort can be added effectively as results accumulate, and they can be embarrassingly parallel. Other methods considered here, such as importance sampling and overlap methods, can be incorporated into thermodynamic integration methods, and can improve the results.

Nevertheless, there are cases where the alternatives to thermodynamic integration would be chosen instead. In the first place, there are many cases where the problem hasn't yet been considered fully enough to establish a natural integration path. But in the second place, it would often be argued that nonspecialized calculations are more efficient because they produce ancillary results too. Furthermore, the success of alternative free energy calculations often depends on some physical insight.

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Chapter
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Publisher: Cambridge University Press
Print publication year: 2006

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  • Generalities
  • Tom L. Beck, University of Cincinnati, Michael E. Paulaitis, The Johns Hopkins University, Lawrence R. Pratt, Los Alamos National Laboratory
  • Book: The Potential Distribution Theorem and Models of Molecular Solutions
  • Online publication: 13 August 2009
  • Chapter DOI: https://doi.org/10.1017/CBO9780511536663.007
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  • Generalities
  • Tom L. Beck, University of Cincinnati, Michael E. Paulaitis, The Johns Hopkins University, Lawrence R. Pratt, Los Alamos National Laboratory
  • Book: The Potential Distribution Theorem and Models of Molecular Solutions
  • Online publication: 13 August 2009
  • Chapter DOI: https://doi.org/10.1017/CBO9780511536663.007
Available formats
×

Save book to Google Drive

To save content items to your account, please confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your account. Find out more about saving content to Google Drive.

  • Generalities
  • Tom L. Beck, University of Cincinnati, Michael E. Paulaitis, The Johns Hopkins University, Lawrence R. Pratt, Los Alamos National Laboratory
  • Book: The Potential Distribution Theorem and Models of Molecular Solutions
  • Online publication: 13 August 2009
  • Chapter DOI: https://doi.org/10.1017/CBO9780511536663.007
Available formats
×