Failure of the work-Hamiltonian connection for free energy calculations

Details Failure of the work-Hamiltonian connection for free energy calculations Failure of the work-Hamiltonian connection for free energy calculations

2007-04-05

arxiv.org/abs/0704.0761v2

Physics

Condensed Matter

Statistical Mechanics

Scientific paper

10.1103/PhysRevLett.100.020601

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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