Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502, Japan.
DISAFA, University of Torino, Largo Paolo Braccini 2, I-10095 Grugliasco, Italy.
J Chem Phys. 2021 Apr 14;154(14):144104. doi: 10.1063/5.0046755.
We develop a detailed theoretical model of photo-induced proton-coupled electron transfer (PPCET) processes, which are at the basis of solar energy harvesting in biological systems and photovoltaic materials. Our model enables us to analyze the dynamics and the efficiency of a PPCET reaction under the influence of a thermal environment by disentangling the contribution of the fundamental electron transfer and proton transfer steps. In order to study quantum dynamics of the PPCET process under an interaction with the non-Markovian environment, we employ the hierarchical equations of motion. We calculate transient absorption spectroscopy (TAS) and a newly defined two-dimensional resonant electronic-vibrational spectroscopy (2DREVS) signals in order to study the nonequilibrium reaction dynamics. Our results show that different transition pathways can be separated by TAS and 2DREVS.
我们开发了一个详细的光诱导质子耦合电子转移（PPCET）过程的理论模型，该模型是生物系统和光伏材料中太阳能收集的基础。我们的模型使我们能够通过分离基本的电子转移和质子转移步骤来分析热环境影响下 PPCET 反应的动力学和效率。为了研究与非马尔可夫环境相互作用下 PPCET 过程的量子动力学，我们采用了层次运动方程。我们计算了瞬态吸收光谱（TAS）和新定义的二维共振电子-振动光谱（2DREVS）信号，以研究非平衡反应动力学。我们的结果表明，TAS 和 2DREVS 可以分离不同的跃迁途径。
