Coherent modified Redfield approach to describe photoinduced proton-coupled electron transfer.

IF 3.1 2区 化学 Q3 CHEMISTRY, PHYSICAL
Charulatha Venkataraman
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引用次数: 0

Abstract

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.

描述光致质子耦合电子转移的相干修正红场方法。
采用相干修正Redfield理论描述了模型哈密顿量下的光致质子耦合电子转移。这种形式主义是Redfield理论的延伸,以捕捉弱到中等的系统池耦合强度,并且动力学是长期的和非马尔可夫的。在模型哈密顿量中,电子与质子和声子池耦合,并最初从地面电子位置光诱导到供体位置。在小能量重整时,系统参数,如供体和受体之间的能量偏差和振动态的重叠,对居群衰变和同位素效应起着至关重要的影响。能量偏置决定了相邻给体-受体能级对之间的间距以及非绝热跃迁中能量有利的受体态。对于我们考虑的模型,质子的施主-受主波函数的重叠比氘的大。当种群初始分布在多个供体振动态时,供体-受体间距越小,H/D种群衰减越快。当氘的间距小于质子的间距时,供体种群衰变表现出逆同位素效应。这些模型表明,在决定人口衰减率方面,间隔和重叠之间存在微妙的平衡。弱电子-声子耦合导致电子居群衰变和质子波包动力学中的相干振荡。较大的耦合强度导致波包局域化和向非相干种群衰减的过渡。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Journal of Chemical Physics
Journal of Chemical Physics 物理-物理:原子、分子和化学物理
CiteScore
7.40
自引率
15.90%
发文量
1615
审稿时长
2 months
期刊介绍: The Journal of Chemical Physics publishes quantitative and rigorous science of long-lasting value in methods and applications of chemical physics. The Journal also publishes brief Communications of significant new findings, Perspectives on the latest advances in the field, and Special Topic issues. The Journal focuses on innovative research in experimental and theoretical areas of chemical physics, including spectroscopy, dynamics, kinetics, statistical mechanics, and quantum mechanics. In addition, topical areas such as polymers, soft matter, materials, surfaces/interfaces, and systems of biological relevance are of increasing importance. Topical coverage includes: Theoretical Methods and Algorithms Advanced Experimental Techniques Atoms, Molecules, and Clusters Liquids, Glasses, and Crystals Surfaces, Interfaces, and Materials Polymers and Soft Matter Biological Molecules and Networks.
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