Jung Kenneth A, Brumer Paul
Chemical Physics Theory Group, Department of Chemistry, and Center for Quantum Information and Quantum Control, University of Toronto, Toronto, Ontario M5S 3H6, Canada.
J Chem Phys. 2020 Sep 21;153(11):114102. doi: 10.1063/5.0020576.
The non-equilibrium stationary coherences that form in donor-acceptor systems are investigated to determine their relationship to the efficiency of energy transfer to a neighboring reaction center. It is found that the effects of asymmetry in the dimer are generally detrimental to the transfer of energy. Four types of systems are examined, arising from combinations of localized trapping, delocalized (Forster) trapping, eigenstate dephasing, and site basis dephasing. In the cases of site basis dephasing, the interplay between the energy gap of the excited dimer states and the environment is shown to give rise to a turnover effect in the efficiency under weak dimer coupling conditions. Furthermore, the nature of the coherences and associated flux is interpreted in terms of pathway interference effects. In addition, regardless of the cases considered, the ratio of the real part and the imaginary part of the coherences in the energy-eigenbasis tends to a constant value in the steady state limit.
研究供体-受体系统中形成的非平衡稳态相干性，以确定它们与向相邻反应中心能量转移效率的关系。发现二聚体中不对称性的影响通常对能量转移不利。研究了四种类型的系统，它们由局域俘获、离域（福斯特）俘获、本征态退相和位点基矢退相的组合产生。在位点基矢退相的情况下，激发二聚体态的能隙与环境之间的相互作用在弱二聚体耦合条件下导致效率出现翻转效应。此外，相干性的性质和相关通量根据路径干涉效应来解释。另外，无论考虑哪种情况，在稳态极限下，能量本征基中相干性的实部与虚部之比趋于一个常数。
