The work-Hamiltonian connection and the usefulness of the Jarzynski equality for free energy calculations
The connection between work and changes in the Hamiltonian for a system with a time-dependent Hamiltonian has recently been called into question, casting doubt on the usefulness of the Jarzynski equality for calculating free energy changes. In this paper, we discuss the relationship between two poss...
| Main Authors: | , |
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| Format: | Article |
| Language: | en_US |
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American Institute of Physics
2013
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| Online Access: | http://hdl.handle.net/1721.1/82536 |
| _version_ | 1811085624933875712 |
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| author | Zimanyi, Eric N. Silbey, Robert J. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Zimanyi, Eric N. Silbey, Robert J. |
| author_sort | Zimanyi, Eric N. |
| collection | MIT |
| description | The connection between work and changes in the Hamiltonian for a system with a time-dependent Hamiltonian has recently been called into question, casting doubt on the usefulness of the Jarzynski equality for calculating free energy changes. In this paper, we discuss the relationship between two possible definitions of free energy and show how some recent disagreements regarding the applicability of the Jarzynski equality are the result of different authors' using different definitions of free energy. Finally, in light of the recently raised doubts, we explicitly demonstrate that it is indeed possible to obtain physically relevant free energy profiles from molecular pulling experiments by using the Jarzynski equality and the results of Hummer and Szabo. |
| first_indexed | 2024-09-23T13:12:14Z |
| format | Article |
| id | mit-1721.1/82536 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T13:12:14Z |
| publishDate | 2013 |
| publisher | American Institute of Physics |
| record_format | dspace |
| spelling | mit-1721.1/825362022-09-28T12:37:16Z The work-Hamiltonian connection and the usefulness of the Jarzynski equality for free energy calculations Zimanyi, Eric N. Silbey, Robert J. Massachusetts Institute of Technology. Department of Chemistry Zimanyi, Eric N. Silbey, Robert J. The connection between work and changes in the Hamiltonian for a system with a time-dependent Hamiltonian has recently been called into question, casting doubt on the usefulness of the Jarzynski equality for calculating free energy changes. In this paper, we discuss the relationship between two possible definitions of free energy and show how some recent disagreements regarding the applicability of the Jarzynski equality are the result of different authors' using different definitions of free energy. Finally, in light of the recently raised doubts, we explicitly demonstrate that it is indeed possible to obtain physically relevant free energy profiles from molecular pulling experiments by using the Jarzynski equality and the results of Hummer and Szabo. National Science Foundation (U.S.) (Grant No. CHE0556268) Fonds québécois de la recherche sur la nature et les technologies 2013-11-21T21:43:09Z 2013-11-21T21:43:09Z 2009-05 2009-02 Article http://purl.org/eprint/type/JournalArticle 00219606 1089-7690 http://hdl.handle.net/1721.1/82536 Zimanyi, Eric N., and Robert J. Silbey. “The work-Hamiltonian connection and the usefulness of the Jarzynski equality for free energy calculations.” The Journal of Chemical Physics 130, no. 17 (2009): 171102. en_US http://dx.doi.org/10.1063/1.3132747 Journal of Chemical Physics Creative Commons Attribution-Noncommercial-Share Alike 3.0 http://creativecommons.org/licenses/by-nc-sa/3.0/ application/pdf American Institute of Physics arXiv |
| spellingShingle | Zimanyi, Eric N. Silbey, Robert J. The work-Hamiltonian connection and the usefulness of the Jarzynski equality for free energy calculations |
| title | The work-Hamiltonian connection and the usefulness of the Jarzynski equality for free energy calculations |
| title_full | The work-Hamiltonian connection and the usefulness of the Jarzynski equality for free energy calculations |
| title_fullStr | The work-Hamiltonian connection and the usefulness of the Jarzynski equality for free energy calculations |
| title_full_unstemmed | The work-Hamiltonian connection and the usefulness of the Jarzynski equality for free energy calculations |
| title_short | The work-Hamiltonian connection and the usefulness of the Jarzynski equality for free energy calculations |
| title_sort | work hamiltonian connection and the usefulness of the jarzynski equality for free energy calculations |
| url | http://hdl.handle.net/1721.1/82536 |
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