System relaxation and thermodynamic integration

Schlitter, J. and Husmeier, D. (1992) System relaxation and thermodynamic integration. Molecular Simulation, 8(3-5), pp. 285-295. (doi: 10.1080/08927029208022483)

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The thermodynamic integration (TI) method for calculating free energy differences has three inherent problems: statistics, numerical integration, and relaxation. In this paper the latter is analyzed for the nonequilibrium TI method introduced by Postma which combines molecular dynamics simulation and TI in a very effective way. A nontrivial extrapolation technique is presented to remove the relaxation error and to calculate the underlying relaxation time. It is shown that the optimal choice of grid points, derived in a previous paper, for minimizing statistical errors not only removes integration errors, but also minimizes relaxation errors. The methods are applied in a calculation of the free energy of cavity formation in water.

Item Type:Articles
Glasgow Author(s) Enlighten ID:Husmeier, Professor Dirk
Authors: Schlitter, J., and Husmeier, D.
College/School:College of Science and Engineering > School of Mathematics and Statistics > Statistics
Journal Name:Molecular Simulation
ISSN (Online):1029-0435

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