Simulation of Solution Phase Electron Transfer in a Compact Donor-Acceptor Dyad
Charge separation (CS) and charge recombination (CR) rates in photosynthetic architectures are difficult to control, yet their ratio can make or break photon-to-current conversion efficiencies. A rational design approach to the enhancement of CS over CR requires a mechanistic understanding of the un...
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| Other Authors: | |
| Format: | Article |
| Language: | en_US |
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American Chemical Society
2012
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| Online Access: | http://hdl.handle.net/1721.1/73955 https://orcid.org/0000-0001-7111-0176 |
| _version_ | 1811068253232955392 |
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| author | Kowalczyk, Timothy Daniel Wang, Lee-Ping Van Voorhis, Troy |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Kowalczyk, Timothy Daniel Wang, Lee-Ping Van Voorhis, Troy |
| author_sort | Kowalczyk, Timothy Daniel |
| collection | MIT |
| description | Charge separation (CS) and charge recombination (CR) rates in photosynthetic architectures are difficult to control, yet their ratio can make or break photon-to-current conversion efficiencies. A rational design approach to the enhancement of CS over CR requires a mechanistic understanding of the underlying electron-transfer (ET) process, including the role of the environment. Toward this goal, we introduce a QM/MM protocol for ET simulations and use it to characterize CR in the formanilide–anthraquinone dyad (FAAQ). Our simulations predict fast recombination of the charge-transfer excited state, in agreement with recent experiments. The computed electronic couplings show an electronic state dependence and are weaker in solution than in the gas phase. We explore the role of cis–trans isomerization on the CR kinetics, and we find strong correlation between the vertical energy gaps of the full simulations and a collective solvent polarization coordinate. Our approach relies on constrained density functional theory to obtain accurate diabatic electronic states on the fly for molecular dynamics simulations, while orientational and electronic polarization of the solvent is captured by a polarizable force field based on a Drude oscillator model. The method offers a unified approach to the characterization of driving forces, reorganization energies, electronic couplings, and nonlinear solvent effects in light-harvesting systems. |
| first_indexed | 2024-09-23T07:53:34Z |
| format | Article |
| id | mit-1721.1/73955 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T07:53:34Z |
| publishDate | 2012 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | mit-1721.1/739552022-09-23T09:26:39Z Simulation of Solution Phase Electron Transfer in a Compact Donor-Acceptor Dyad Kowalczyk, Timothy Daniel Wang, Lee-Ping Van Voorhis, Troy Massachusetts Institute of Technology. Department of Chemistry Van Voorhis, Troy Kowalczyk, Timothy Daniel Wang, Lee-Ping Van Voorhis, Troy Charge separation (CS) and charge recombination (CR) rates in photosynthetic architectures are difficult to control, yet their ratio can make or break photon-to-current conversion efficiencies. A rational design approach to the enhancement of CS over CR requires a mechanistic understanding of the underlying electron-transfer (ET) process, including the role of the environment. Toward this goal, we introduce a QM/MM protocol for ET simulations and use it to characterize CR in the formanilide–anthraquinone dyad (FAAQ). Our simulations predict fast recombination of the charge-transfer excited state, in agreement with recent experiments. The computed electronic couplings show an electronic state dependence and are weaker in solution than in the gas phase. We explore the role of cis–trans isomerization on the CR kinetics, and we find strong correlation between the vertical energy gaps of the full simulations and a collective solvent polarization coordinate. Our approach relies on constrained density functional theory to obtain accurate diabatic electronic states on the fly for molecular dynamics simulations, while orientational and electronic polarization of the solvent is captured by a polarizable force field based on a Drude oscillator model. The method offers a unified approach to the characterization of driving forces, reorganization energies, electronic couplings, and nonlinear solvent effects in light-harvesting systems. Chesonis Family Foundation (Solar Revolution Project Fellowship) eni-MIT Solar Frontiers Center (Solar Frontiers Research Program) 2012-10-15T14:25:22Z 2012-10-15T14:25:22Z 2011-09 2011-08 Article http://purl.org/eprint/type/JournalArticle 1520-6106 1520-5207 http://hdl.handle.net/1721.1/73955 Kowalczyk, Tim, Lee-Ping Wang, and Troy Van Voorhis. “Simulation of Solution Phase Electron Transfer in a Compact Donor–Acceptor Dyad.” The Journal of Physical Chemistry B 115.42 (2011): 12135–12144. Web. https://orcid.org/0000-0001-7111-0176 en_US http://dx.doi.org/ 10.1021/jp204962k Journal of Physical Chemistry B 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 Prof. van Voorhis via Erja Kajosalo |
| spellingShingle | Kowalczyk, Timothy Daniel Wang, Lee-Ping Van Voorhis, Troy Simulation of Solution Phase Electron Transfer in a Compact Donor-Acceptor Dyad |
| title | Simulation of Solution Phase Electron Transfer in a Compact Donor-Acceptor Dyad |
| title_full | Simulation of Solution Phase Electron Transfer in a Compact Donor-Acceptor Dyad |
| title_fullStr | Simulation of Solution Phase Electron Transfer in a Compact Donor-Acceptor Dyad |
| title_full_unstemmed | Simulation of Solution Phase Electron Transfer in a Compact Donor-Acceptor Dyad |
| title_short | Simulation of Solution Phase Electron Transfer in a Compact Donor-Acceptor Dyad |
| title_sort | simulation of solution phase electron transfer in a compact donor acceptor dyad |
| url | http://hdl.handle.net/1721.1/73955 https://orcid.org/0000-0001-7111-0176 |
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