A Polarizable QM/MM Explicit Solvent Model for Computational Electrochemistry in Water
We present a quantum mechanical/molecular mechanical (QM/MM) explicit solvent model for the computation of standard reduction potentials E[subscript 0]. The QM/MM model uses density functional theory (DFT) to model the solute and a polarizable molecular mechanics (MM) force field to describe the sol...
| Váldodahkkit: | , |
|---|---|
| Eará dahkkit: | |
| Materiálatiipa: | Artihkal |
| Giella: | en_US |
| Almmustuhtton: |
American Chemical Society (ACS)
2013
|
| Liŋkkat: | http://hdl.handle.net/1721.1/76274 https://orcid.org/0000-0001-7111-0176 |
| _version_ | 1826191264797687808 |
|---|---|
| author | Wang, Lee-Ping Voorhis, Troy Van |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Wang, Lee-Ping Voorhis, Troy Van |
| author_sort | Wang, Lee-Ping |
| collection | MIT |
| description | We present a quantum mechanical/molecular mechanical (QM/MM) explicit solvent model for the computation of standard reduction potentials E[subscript 0]. The QM/MM model uses density functional theory (DFT) to model the solute and a polarizable molecular mechanics (MM) force field to describe the solvent. The linear response approximation is applied to estimate E[subscript 0] from the thermally averaged electron attachment/detachment energies computed in the oxidized and reduced states. Using the QM/MM model, we calculated one-electron E[subscript 0] values for several aqueous transition-metal complexes and found substantially improved agreement with experiment compared to values obtained from implicit solvent models. A detailed breakdown of the physical effects in the QM/MM model indicates that hydrogen-bonding effects are mainly responsible for the differences in computed values of E[subscript 0] between the QM/MM and implicit models. Our results highlight the importance of including solute–solvent hydrogen-bonding effects in the theoretical modeling of redox processes. |
| first_indexed | 2024-09-23T08:53:11Z |
| format | Article |
| id | mit-1721.1/76274 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T08:53:11Z |
| publishDate | 2013 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/762742022-09-26T08:56:33Z A Polarizable QM/MM Explicit Solvent Model for Computational Electrochemistry in Water Wang, Lee-Ping Voorhis, Troy Van Massachusetts Institute of Technology. Department of Chemistry Van Voorhis, Troy Wang, Lee-Ping Voorhis, Troy Van We present a quantum mechanical/molecular mechanical (QM/MM) explicit solvent model for the computation of standard reduction potentials E[subscript 0]. The QM/MM model uses density functional theory (DFT) to model the solute and a polarizable molecular mechanics (MM) force field to describe the solvent. The linear response approximation is applied to estimate E[subscript 0] from the thermally averaged electron attachment/detachment energies computed in the oxidized and reduced states. Using the QM/MM model, we calculated one-electron E[subscript 0] values for several aqueous transition-metal complexes and found substantially improved agreement with experiment compared to values obtained from implicit solvent models. A detailed breakdown of the physical effects in the QM/MM model indicates that hydrogen-bonding effects are mainly responsible for the differences in computed values of E[subscript 0] between the QM/MM and implicit models. Our results highlight the importance of including solute–solvent hydrogen-bonding effects in the theoretical modeling of redox processes. Eni S.p.A 2013-01-17T14:13:57Z 2013-01-17T14:13:57Z 2012-01 2011-05 Article http://purl.org/eprint/type/JournalArticle 1549-9618 1549-9626 http://hdl.handle.net/1721.1/76274 Wang, Lee-Ping, and Troy Van Voorhis. “A Polarizable QM/MM Explicit Solvent Model for Computational Electrochemistry in Water.” Journal of Chemical Theory and Computation 8.2 (2012): 610–617. https://orcid.org/0000-0001-7111-0176 en_US http://dx.doi.org/10.1021/ct200340x 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 | Wang, Lee-Ping Voorhis, Troy Van A Polarizable QM/MM Explicit Solvent Model for Computational Electrochemistry in Water |
| title | A Polarizable QM/MM Explicit Solvent Model for Computational Electrochemistry in Water |
| title_full | A Polarizable QM/MM Explicit Solvent Model for Computational Electrochemistry in Water |
| title_fullStr | A Polarizable QM/MM Explicit Solvent Model for Computational Electrochemistry in Water |
| title_full_unstemmed | A Polarizable QM/MM Explicit Solvent Model for Computational Electrochemistry in Water |
| title_short | A Polarizable QM/MM Explicit Solvent Model for Computational Electrochemistry in Water |
| title_sort | polarizable qm mm explicit solvent model for computational electrochemistry in water |
| url | http://hdl.handle.net/1721.1/76274 https://orcid.org/0000-0001-7111-0176 |
| work_keys_str_mv | AT wangleeping apolarizableqmmmexplicitsolventmodelforcomputationalelectrochemistryinwater AT voorhistroyvan apolarizableqmmmexplicitsolventmodelforcomputationalelectrochemistryinwater AT wangleeping polarizableqmmmexplicitsolventmodelforcomputationalelectrochemistryinwater AT voorhistroyvan polarizableqmmmexplicitsolventmodelforcomputationalelectrochemistryinwater |