Adiabatic Approximation in Explicit Solvent Models of RedOx Chemistry
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 const...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2018
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| Online Access: | http://hdl.handle.net/1721.1/115111 https://orcid.org/0000-0003-1487-2910 https://orcid.org/0000-0001-7111-0176 |
| _version_ | 1811095527744339968 |
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| author | Vaissier, Valerie Van Voorhis, Troy |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Vaissier, Valerie Van Voorhis, Troy |
| author_sort | Vaissier, Valerie |
| collection | MIT |
| description | 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. |
| first_indexed | 2024-09-23T16:18:53Z |
| format | Article |
| id | mit-1721.1/115111 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T16:18:53Z |
| publishDate | 2018 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1151112022-09-29T19:31:51Z Adiabatic Approximation in Explicit Solvent Models of RedOx Chemistry Vaissier, Valerie Van Voorhis, Troy Massachusetts Institute of Technology. Department of Chemistry Voorhis, Troy Van Vaissier, Valerie Van Voorhis, Troy 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. National Science Foundation (U.S.) (Grant CHE-1058219) 2018-04-30T18:55:15Z 2018-04-30T18:55:15Z 2016-09 2016-07 Article http://purl.org/eprint/type/JournalArticle 1549-9618 1549-9626 http://hdl.handle.net/1721.1/115111 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 https://orcid.org/0000-0003-1487-2910 https://orcid.org/0000-0001-7111-0176 en_US https://pubs.acs.org/doi/10.1021/acs.jctc.6b00746 Journal of Chemical Theory and Computation 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. application/pdf American Chemical Society (ACS) Prof. Van Voorhis via Erja Kajosalo |
| spellingShingle | Vaissier, Valerie Van Voorhis, Troy Adiabatic Approximation in Explicit Solvent Models of RedOx Chemistry |
| title | Adiabatic Approximation in Explicit Solvent Models of RedOx Chemistry |
| title_full | Adiabatic Approximation in Explicit Solvent Models of RedOx Chemistry |
| title_fullStr | Adiabatic Approximation in Explicit Solvent Models of RedOx Chemistry |
| title_full_unstemmed | Adiabatic Approximation in Explicit Solvent Models of RedOx Chemistry |
| title_short | Adiabatic Approximation in Explicit Solvent Models of RedOx Chemistry |
| title_sort | adiabatic approximation in explicit solvent models of redox chemistry |
| url | http://hdl.handle.net/1721.1/115111 https://orcid.org/0000-0003-1487-2910 https://orcid.org/0000-0001-7111-0176 |
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