Spectroscopic photorelaxation signatures in pyrazine from nonadiabatic dynamics simulations with coupled cluster theory

Abstract

Despite extensive theoretical and experimental efforts, the mechanisms underlying the ultrafast relaxation of pyrazine after photoexcitation remain challenging to disentangle. Recently, theoretical investigations have been converging towards a three-state mechanism, with an ultrafast decay of the bright ${}^{1}B_{2u}$ state followed by beats in the populations of the low-lying ${}^{1}B_{3u}$ and ${}^{1}A_u$ states. However, a clear agreement between the experimental results and the corresponding theoretical predictions remains elusive. Here, we present a high-level simulation of the ultrafast excited states dynamics of pyrazine using coupled cluster theory with single and double excitations and ab initio multiple spawning, together with predictions of the time-resolved photoelectron spectrum and X-ray absorption spectra at the nitrogen and carbon edges. This is made possible by using a newly developed multistate implementation of similarity constrained coupled cluster theory. We find quantitative agreement with the experimental signature of the ${}^{1}B_{2u}$ decay in the photoelectron spectrum, and qualitative agreement with the available experimental X-ray absorption spectra. Moreover, we detail spectroscopic signatures that should be verifiable in experiments with sufficient resolution in the time and frequency domains. Compared to previous theoretical studies, we provide further detailed insight into the interplay of the states involved in the photorelaxation.