Probing photoinduced proton coupled electron transfer process by means of two-dimensional resonant electronic-vibrational spectroscopy

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.

Automated summary

In this study, a detailed theoretical model of photo-induced proton-coupled electron transfer (PPCET) processes was developed to analyze the dynamics and efficiency of the reaction. By employing hierarchical equations of motion, the quantum dynamics of the PPCET process under an interaction with a non-Markovian environment was studied, providing insights into the transition pathways through transient absorption spectroscopy (TAS) and two-dimensional resonant electronic-vibrational spectroscopy (2DREVS) signals.