Failure of the work-hamiltonian connection for free-energy calculations Journal Article
| Authors: | Vilar, J. M. G.; Rubi, J. M. |
| Article Title: | Failure of the work-hamiltonian connection for free-energy calculations |
| Abstract: | Extensions of statistical mechanics are routinely being used to infer free energies from the work performed over single-molecule nonequilibrium trajectories. A key element of this approach is the ubiquitous expression dW/dt= H(x,t) t, which connects the microscopic work W performed by a time-dependent force on the coordinate x with the corresponding Hamiltonian H(x,t) at time t. Here we show that this connection, as pivotal as it is, cannot be used to estimate free-energy changes. We discuss the implications of this result for single-molecule experiments and atomistic molecular simulations and point out possible avenues to overcome these limitations. © 2008 The American Physical Society. |
| Keywords: | computer simulation; molecular physics; statistical mechanics; hamiltonians; ubiquitous computing; atomistic molecular simulations; single-molecule nonequilibrium; free energy |
| Journal Title: | Physical Review Letters |
| Volume: | 100 |
| Issue: | 2 |
| ISSN: | 0031-9007 |
| Publisher: | American Physical Society |
| Date Published: | 2008-01-18 |
| Start Page: | 020601 |
| Language: | English |
| DOI: | 10.1103/PhysRevLett.100.020601 |
| PROVIDER: | scopus |
| PUBMED: | 18232843 |
| DOI/URL: | |
| Notes: | --- - "Cited By (since 1996): 4" - "Export Date: 17 November 2011" - "CODEN: PRLTA" - "Source: Scopus" |
