Minimizing thermodynamic length to select intermediate states for free-energy calculations and replica-exchange simulations.
In computational thermodynamics, a sequence of intermediate states is commonly introduced to connect two equilibrium states. We consider two cases where the choice of intermediate states is particularly important: minimizing statistical error in free-energy difference calculations and maximizing average acceptance probabilities in replica-exchange simulations. We derive bounds for these quantities in terms of the thermodynamic distance between the intermediates, and show that in both cases the intermediates should be chosen as equidistant points along a geodesic connecting the end states.
Shenfeld
Daniel K
DK
D E Shaw Research, New York, New York 10036, USA.
Xu
Huafeng
H
Eastwood
Michael P
MP
Dror
Ron O
RO
Shaw
David E
DE
D003198:Computer Simulation; D004735:Energy Transfer; D008962:Models, Theoretical; D009716:Numerical Analysis, Computer-Assisted; D013816:Thermodynamics