Vilar, J. M. G. (José M. G.), 1972-Rubí Capaceti, José Miguel2019-05-302019-05-302008-01-160031-9007https://hdl.handle.net/2445/134218Extensions 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 d W / d t = ∂ 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.4 p.application/pdfeng(c) American Physical Society, 2008Mecànica estadísticaMolèculesStatistical mechanicsMoleculesinfo:eu-repo/semantics/article6047392019-05-30info:eu-repo/semantics/openAccess