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Suppression of Charge Recombination by Auxiliary Atoms in Photoinduced Charge Separation Dynamics with Mn Oxides: A Theoretical Study
Charge separation is one of the most crucial processes in photochemical dynamics of energy conversion, widely observed ranging from water splitting in photosystem II (PSII) of plants to photoinduced oxidation reduction processes. Several basic principles, with respect to charge separation, are known...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8838452/ https://www.ncbi.nlm.nih.gov/pubmed/35164020 http://dx.doi.org/10.3390/molecules27030755 |
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author | Ohnishi, Yu Yamamoto, Kentaro Takatsuka, Kazuo |
author_facet | Ohnishi, Yu Yamamoto, Kentaro Takatsuka, Kazuo |
author_sort | Ohnishi, Yu |
collection | PubMed |
description | Charge separation is one of the most crucial processes in photochemical dynamics of energy conversion, widely observed ranging from water splitting in photosystem II (PSII) of plants to photoinduced oxidation reduction processes. Several basic principles, with respect to charge separation, are known, each of which suffers inherent charge recombination channels that suppress the separation efficiency. We found a charge separation mechanism in the photoinduced excited-state proton transfer dynamics from Mn oxides to organic acceptors. This mechanism is referred to as coupled proton and electron wave-packet transfer (CPEWT), which is essentially a synchronous transfer of electron wave-packets and protons through mutually different spatial channels to separated destinations passing through nonadiabatic regions, such as conical intersections, and avoided crossings. CPEWT also applies to collision-induced ground-state water splitting dynamics catalyzed by Mn(4)CaO(5) cluster. For the present photoinduced charge separation dynamics by Mn oxides, we identified a dynamical mechanism of charge recombination. It takes place by passing across nonadiabatic regions, which are different from those for charge separations and lead to the excited states of the initial state before photoabsorption. This article is an overview of our work on photoinduced charge separation and associated charge recombination with an additional study. After reviewing the basic mechanisms of charge separation and recombination, we herein studied substituent effects on the suppression of such charge recombination by doping auxiliary atoms. Our illustrative systems are X–Mn(OH)(2) tied to N-methylformamidine, with X=OH, Be(OH)(3), Mg(OH)(3), Ca(OH)(3), Sr(OH)(3) along with Al(OH)(4) and Zn(OH)(3). We found that the competence of suppression of charge recombination depends significantly on the substituents. The present study should serve as a useful guiding principle in designing the relevant photocatalysts. |
format | Online Article Text |
id | pubmed-8838452 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-88384522022-02-13 Suppression of Charge Recombination by Auxiliary Atoms in Photoinduced Charge Separation Dynamics with Mn Oxides: A Theoretical Study Ohnishi, Yu Yamamoto, Kentaro Takatsuka, Kazuo Molecules Article Charge separation is one of the most crucial processes in photochemical dynamics of energy conversion, widely observed ranging from water splitting in photosystem II (PSII) of plants to photoinduced oxidation reduction processes. Several basic principles, with respect to charge separation, are known, each of which suffers inherent charge recombination channels that suppress the separation efficiency. We found a charge separation mechanism in the photoinduced excited-state proton transfer dynamics from Mn oxides to organic acceptors. This mechanism is referred to as coupled proton and electron wave-packet transfer (CPEWT), which is essentially a synchronous transfer of electron wave-packets and protons through mutually different spatial channels to separated destinations passing through nonadiabatic regions, such as conical intersections, and avoided crossings. CPEWT also applies to collision-induced ground-state water splitting dynamics catalyzed by Mn(4)CaO(5) cluster. For the present photoinduced charge separation dynamics by Mn oxides, we identified a dynamical mechanism of charge recombination. It takes place by passing across nonadiabatic regions, which are different from those for charge separations and lead to the excited states of the initial state before photoabsorption. This article is an overview of our work on photoinduced charge separation and associated charge recombination with an additional study. After reviewing the basic mechanisms of charge separation and recombination, we herein studied substituent effects on the suppression of such charge recombination by doping auxiliary atoms. Our illustrative systems are X–Mn(OH)(2) tied to N-methylformamidine, with X=OH, Be(OH)(3), Mg(OH)(3), Ca(OH)(3), Sr(OH)(3) along with Al(OH)(4) and Zn(OH)(3). We found that the competence of suppression of charge recombination depends significantly on the substituents. The present study should serve as a useful guiding principle in designing the relevant photocatalysts. MDPI 2022-01-24 /pmc/articles/PMC8838452/ /pubmed/35164020 http://dx.doi.org/10.3390/molecules27030755 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Ohnishi, Yu Yamamoto, Kentaro Takatsuka, Kazuo Suppression of Charge Recombination by Auxiliary Atoms in Photoinduced Charge Separation Dynamics with Mn Oxides: A Theoretical Study |
title | Suppression of Charge Recombination by Auxiliary Atoms in Photoinduced Charge Separation Dynamics with Mn Oxides: A Theoretical Study |
title_full | Suppression of Charge Recombination by Auxiliary Atoms in Photoinduced Charge Separation Dynamics with Mn Oxides: A Theoretical Study |
title_fullStr | Suppression of Charge Recombination by Auxiliary Atoms in Photoinduced Charge Separation Dynamics with Mn Oxides: A Theoretical Study |
title_full_unstemmed | Suppression of Charge Recombination by Auxiliary Atoms in Photoinduced Charge Separation Dynamics with Mn Oxides: A Theoretical Study |
title_short | Suppression of Charge Recombination by Auxiliary Atoms in Photoinduced Charge Separation Dynamics with Mn Oxides: A Theoretical Study |
title_sort | suppression of charge recombination by auxiliary atoms in photoinduced charge separation dynamics with mn oxides: a theoretical study |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8838452/ https://www.ncbi.nlm.nih.gov/pubmed/35164020 http://dx.doi.org/10.3390/molecules27030755 |
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