A general method is introduced for the calculation of the free-energy difference between two systems,0 and 1,with configuration spaces OMEGA~((0)),OMEGA~((1)) of the same dimensionality.The method relies upon establishing a bijective mapping between disjoint subsets GAMMA_i~((0)) of OMEGA~((0)) and corresponding disjoint subsets GAMMA_i~((1)) of OMEGA~((1)) and averaging a function of the ratio of configurational integrals over GAMMA_i~((0)) and GAMMA_i~((1)) with respect to the probability densities of the two systems.The mapped subsets GAMMA_i~((0)) and GAMMA_i~((1)) need not span the entire configuration spaces OMEGA~((0)) and OMEGA~((1)).The method is applied for the calculation of the excess chemical potential mu~(ex) in a Lennard-Jones (LJ) fluid.In this case,OMEGA~((0)) is the configuration space of a (N-1) real molecule plus one ideal-gas molecule system,while OMEGA~((1)) is the configuration space of a N real molecule system occupying the same volume.GAMMA_i~((0)) and GAMMA_i~((1)) are constructed from hyperspheres of the same radius centered at minimum-energy configurations of a set of "active" molecules lying within distance a from the ideal-gas molecule and the last real molecule,respectively.An algorithm is described for sampling GAMMA_i~((0)) and GAMMA_i~((1)) given a point in OMEGA~((0)) or in OMEGA~((1)).The algorithm encompasses three steps: "quenching" (minimization with respect to the active-molecule degrees of freedom),"mutation" (gradual conversion of the ideal-gas molecule into a real molecule,with simultaneous minimization of the energy with respect to the active-molecule degrees of freedom),and "excitation" (generation of points on a hypersphere centered at the active-molecule energy minimum).These steps are also carried out in reverse,as required by the bijective nature of the mapping.The mutation step,which establishes a reversible mapping between energy minima with respect to the active degrees of freedom of systems 0 and 1,ensures that excluded volume interactions emerging in the process of converting the ideal-gas molecule into a real molecule are relieved through appropriate rearrangement of the surrounding active molecules.Thus,the insertion problem plaguing traditional methods for the calculation of chemical potential at high densities is alleviated.Results are presented at two state points of the LJ system for a variety of radii a of the active domain.It is shown that the estimated values of mu~(ex) are correct in all cases and subject to an order of magnitude lower statistical uncertainty than values based on the same number of Widom [J.Chem.Phys.39,2808 (1963)] insertions at high fluid densities.Optimal settings for the new algorithm are identified and distributions of the quantities involved in it [number of active molecules,energy at the sampled minima of systems 0 and 1,and free-energy differences between subsets GAMMA_i~((0)) and GAMMA_i~((1)) that are mapped onto each other] are explored.
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