On Finite-Size Corrections to the Free Energy of Ionic Hydration
Efforts to compare thermodynamic predictions of simulations with experiment have been thwarted by the approximations used in modeling the long-range electrostatic interactions. In a recent article Hummer et al. proposed an explicit formula that accounts for most of the finite-size effect in simulati...
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Published in | The journal of physical chemistry. B Vol. 101; no. 29; pp. 5622 - 5623 |
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Main Authors | , , |
Format | Journal Article |
Language | English |
Published |
American Chemical Society
17.07.1997
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Online Access | Get full text |
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Summary: | Efforts to compare thermodynamic predictions of simulations with experiment have been thwarted by the approximations used in modeling the long-range electrostatic interactions. In a recent article Hummer et al. proposed an explicit formula that accounts for most of the finite-size effect in simulations of ion charging using periodic boundary conditions. In this Letter we have verified the numerical results of Hummer et al. and we provide a simple theoretical argument that explains why the solvent polarization free energy contains a contribution that largely cancels the lattice self-energy. The cancellation depends on the fact that the solvent is a high dielectric. We propose a finite size correction formula that can be applied in both the low and high dielectric limits. |
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Bibliography: | istex:A4476022E4D411DDC5B577D5D0F939B56857EF2B ark:/67375/TPS-97WZ8ZNH-K Abstract published in Advance ACS Abstracts, June 15, 1997. |
ISSN: | 1520-6106 1520-5207 |
DOI: | 10.1021/jp970882x |