{"title":"描述光致质子耦合电子转移的相干修正红场方法。","authors":"Charulatha Venkataraman","doi":"10.1063/5.0286825","DOIUrl":null,"url":null,"abstract":"<p><p>Coherent modified Redfield theory is employed to describe photoinduced proton-coupled electron transfer for a model Hamiltonian. This formalism is an extension of Redfield theory to capture weak to moderate system-bath coupling strengths, and the dynamics is secular and non-Markovian. In the model Hamiltonian, the electron is coupled to the proton and a phonon bath and is initially photoinduced from the ground electronic site to a donor site. At small bath reorganization energies, the system parameters, such as the energy bias between the donor and acceptor sites and overlaps of the vibronic states, play a crucial role in influencing the population decay and isotope effect. The energy bias decides the spacing between adjacent pairs of donor-acceptor levels as well as the energetically favorable acceptor states for the non-adiabatic transition. For the models we considered, the overlaps of the donor-acceptor wavefunctions of the proton are larger than those of deuterium. When the population is initially distributed over several donor vibrational states, the H/D population decays faster for the case that has the smaller adjacent donor-acceptor spacing. The donor population decay shows an inverse isotope effect when this spacing is smaller for deuterium than for protons. These models demonstrate a subtle balance between the spacing and overlaps in deciding the rate of population decay. Weak electron-phonon coupling leads to coherent oscillations in the electronic population decay and proton wavepacket dynamics. Larger coupling strengths lead to wavepacket localization and the transition to incoherent population decay.</p>","PeriodicalId":15313,"journal":{"name":"Journal of Chemical Physics","volume":"163 8","pages":""},"PeriodicalIF":3.1000,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Coherent modified Redfield approach to describe photoinduced proton-coupled electron transfer.\",\"authors\":\"Charulatha Venkataraman\",\"doi\":\"10.1063/5.0286825\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Coherent modified Redfield theory is employed to describe photoinduced proton-coupled electron transfer for a model Hamiltonian. This formalism is an extension of Redfield theory to capture weak to moderate system-bath coupling strengths, and the dynamics is secular and non-Markovian. In the model Hamiltonian, the electron is coupled to the proton and a phonon bath and is initially photoinduced from the ground electronic site to a donor site. At small bath reorganization energies, the system parameters, such as the energy bias between the donor and acceptor sites and overlaps of the vibronic states, play a crucial role in influencing the population decay and isotope effect. The energy bias decides the spacing between adjacent pairs of donor-acceptor levels as well as the energetically favorable acceptor states for the non-adiabatic transition. For the models we considered, the overlaps of the donor-acceptor wavefunctions of the proton are larger than those of deuterium. When the population is initially distributed over several donor vibrational states, the H/D population decays faster for the case that has the smaller adjacent donor-acceptor spacing. The donor population decay shows an inverse isotope effect when this spacing is smaller for deuterium than for protons. These models demonstrate a subtle balance between the spacing and overlaps in deciding the rate of population decay. Weak electron-phonon coupling leads to coherent oscillations in the electronic population decay and proton wavepacket dynamics. Larger coupling strengths lead to wavepacket localization and the transition to incoherent population decay.</p>\",\"PeriodicalId\":15313,\"journal\":{\"name\":\"Journal of Chemical Physics\",\"volume\":\"163 8\",\"pages\":\"\"},\"PeriodicalIF\":3.1000,\"publicationDate\":\"2025-08-28\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Chemical Physics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1063/5.0286825\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1063/5.0286825","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Coherent modified Redfield approach to describe photoinduced proton-coupled electron transfer.
Coherent modified Redfield theory is employed to describe photoinduced proton-coupled electron transfer for a model Hamiltonian. This formalism is an extension of Redfield theory to capture weak to moderate system-bath coupling strengths, and the dynamics is secular and non-Markovian. In the model Hamiltonian, the electron is coupled to the proton and a phonon bath and is initially photoinduced from the ground electronic site to a donor site. At small bath reorganization energies, the system parameters, such as the energy bias between the donor and acceptor sites and overlaps of the vibronic states, play a crucial role in influencing the population decay and isotope effect. The energy bias decides the spacing between adjacent pairs of donor-acceptor levels as well as the energetically favorable acceptor states for the non-adiabatic transition. For the models we considered, the overlaps of the donor-acceptor wavefunctions of the proton are larger than those of deuterium. When the population is initially distributed over several donor vibrational states, the H/D population decays faster for the case that has the smaller adjacent donor-acceptor spacing. The donor population decay shows an inverse isotope effect when this spacing is smaller for deuterium than for protons. These models demonstrate a subtle balance between the spacing and overlaps in deciding the rate of population decay. Weak electron-phonon coupling leads to coherent oscillations in the electronic population decay and proton wavepacket dynamics. Larger coupling strengths lead to wavepacket localization and the transition to incoherent population decay.
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