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Ewald sum corrections in simulations of ion and dipole solvation and electron transfer
The Journal of Chemical Physics ( IF 4.4 ) Pub Date : 2021-09-17 , DOI: 10.1063/5.0061644
Dmitry V Matyushov 1
Affiliation  

Periodic boundary conditions and Ewald sums used in standard simulation protocols require finite-size corrections when the total charge of the simulated system is nonzero. Corrections for ion solvation were introduced by Hummer, Pratt, and García, [J. Chem. Phys. 107, 9275 (1997)]. The latter approach is extended here to derive finite-size correction for the Stokes-shift and reorganization energy applied to electron-transfer reactions. The same correction term, scaling inversely with the box size, adds to the reorganization energy from the energy-gap variance but is subtracted from the reorganization energy calculated from the Stokes shift. Finite-size corrections thus widen the gap between these two quantities, which were recently found to diverge for protein electron transfer. Corrections to the free energy of dipole solvation and the variance of the electric field scale as m2/L3 with the solute dipole m and the box size L.

中文翻译:

离子和偶极子溶剂化和电子转移模拟中的 Ewald sum 校正

当模拟系统的总电荷非零时,标准模拟协议中使用的周期性边界条件和 Ewald 和需要有限大小的修正。Hummer、Pratt 和 García 介绍了对离子溶剂化的修正,[J. 化学 物理。107, 9275 (1997)]。后一种方法在此处扩展为对应用于电子转移反应的斯托克斯位移和重组能量进行有限尺寸校正。相同的校正项与框大小成反比,从能隙方差增加重组能量,但从斯托克斯位移计算的重组能量中减去。因此,有限尺寸校正扩大了这两个数量之间的差距,最近发现这两个数量在蛋白质电子转移方面存在分歧。m 2 / L 3具有溶质偶极子m和盒子尺寸L
更新日期:2021-09-21
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