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Failure of the work-Hamiltonian connection for free energy calculations

Authors
  • Vilar, Jose M. G.
  • Rubi, J. Miguel
Type
Preprint
Publication Date
Apr 08, 2007
Submission Date
Apr 05, 2007
Identifiers
DOI: 10.1103/PhysRevLett.100.020601
Source
arXiv
License
Unknown
External links

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=\partial H(x,t)/ \partial 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.

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