TY - JOUR

T1 - Satisfying the fluctuation theorem in free-energy calculations with Hamiltonian replica exchange

AU - Wyczalkowski, Matthew A.

AU - Pappu, Rohit V.

PY - 2008/2/20

Y1 - 2008/2/20

N2 - An error measure, referred to as the hysteresis error, is developed from the Crooks fluctuation theorem to evaluate the sampling quality in free-energy calculations. Theory and the numerical free energy of hydration calculations are used to show that Hamiltonian replica exchange provides a direct route for minimizing the hysteresis error. Replica exchange swap probabilities yield the rate at which the hysteresis error falls with the simulation length, and this result can be used to decrease bias and statistical errors associated with free-energy calculations based on multicanonical simulations.

AB - An error measure, referred to as the hysteresis error, is developed from the Crooks fluctuation theorem to evaluate the sampling quality in free-energy calculations. Theory and the numerical free energy of hydration calculations are used to show that Hamiltonian replica exchange provides a direct route for minimizing the hysteresis error. Replica exchange swap probabilities yield the rate at which the hysteresis error falls with the simulation length, and this result can be used to decrease bias and statistical errors associated with free-energy calculations based on multicanonical simulations.

UR - http://www.scopus.com/inward/record.url?scp=40549083345&partnerID=8YFLogxK

U2 - 10.1103/PhysRevE.77.026104

DO - 10.1103/PhysRevE.77.026104

M3 - Article

C2 - 18352087

AN - SCOPUS:40549083345

SN - 1539-3755

VL - 77

JO - Physical Review E - Statistical, Nonlinear, and Soft Matter Physics

JF - Physical Review E - Statistical, Nonlinear, and Soft Matter Physics

IS - 2

M1 - 026104

ER -