The Journal of Physical Chemistry B · 2005 · 104 citations · 10 references
Natural SciencesPhysicsMathematical PhysicsMolecular PhysicsThermodynamicsChemical ThermodynamicsFree EnergyNon-equilibrium ThermodynamicsStatistical MechanicsStatistical ThermodynamicsThermodynamic PropertiesChemical NonequilibriumIdeal Gas Equation Of StateMaxwell ModelNon-equilibrium Statistical MechanicsNonequilibrium DynamicsStatistical Foundations Of ThermodynamicsStatistical Mechanics Of Molecular SystemsUltracold Molecules
We suggest and discuss a simple model of an ideal gas under the piston to gain an insight into the workings of the Jarzynski identity connecting the average exponential of the work over the nonequilibrium trajectories with the equilibrium free energy. We show that the identity is valid for our system, due to the very rapid molecules belonging to the tail of the Maxwell distribution. For the most interesting extreme, when the system volume is large, while the piston is moving with great speed (compared to thermal velocity) for a very short time, the necessary number of independent experimental runs to obtain a reasonable approximation for the free energy from averaging the nonequilibrium work grows exponentially with the system size.
10
Nonequilibrium Equality for Free Energy Differences
Christopher Jarzynski · Physical Review Letters · 1997 · 5.4K citations · Full text
Jan Liphardt, Sophie Dumont, Steven B. Smith et al. · Science · 2002 · 1.3K citations
Fluctuation theorem for stochastic dynamics
Jorge Kurchan · Journal of Physics A Mathematical and General · 1998 · 1.1K citations · Full text