Adiabatic Approximation in Explicit Solvent Models of RedOx Chemistry
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Vaissier16JCTC.pdf
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Author(s)
Vaissier, Valerie
Van Voorhis, Troy
Date Issued
September 2016
Journal
Journal of Chemical Theory and Computation
Publisher
American Chemical Society (ACS)
Citation
Vaissier, Valérie and Troy Van Voorhis. “Adiabatic Approximation in Explicit Solvent Models of RedOx Chemistry.” Journal of Chemical Theory and Computation 12, 10 (September 2016): 5111–5116 © 2016 American Chemical Society
Version
Author's final manuscript
Abstract
We propose a calculation scheme that accelerates QM/MM simulations of solvated systems. This new approach is based on the adiabatic approximation whereby the solute degrees of freedom are separated from those of the solvent. More specifically, we assume that the solute electron density remains constant with respect to the relaxation of the solvent molecules. This allows us to achieve a dramatic speed-up of QM/MM calculations by discarding the slow self-consistent field cycle. We test this method by applying it to the calculation of the redox potential of aqueous transition metal ions. The root-mean-square deviation (RMSD) between the full solvation and adiabatic approximation is only 0.17 V. We find a RMSD from experimental values of 0.32 V for the adiabatic approximation as compared to 0.31 V for the full solvation model, so that the two methods are of essentially the same accuracy. Meanwhile, the adiabatic calculations are up to 10 times faster than the full solvation calculations, meaning that the method proposed here reduces the cost of QM/MM calculations while retaining the accuracy.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
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DOI of Published Version
https://doi.org/10.1021/acs.jctc.6b00746
