Identification of an ultrafast internal conversion pathway of pyrazine by time-resolved vacuum ultraviolet photoelectron spectrum simulations

Abstract: The internal conversion from the optically bright S$<em>2$ ($^1$B$</em>{2\mathrm{u}}$, $\pi\pi<sup>*$) state to the dark S$<em>1$ ($^1$B$</em>{3\mathrm{u}}$, n$\pi<sup>*$) state in pyrazine is a standard benchmark for experimental and theoretical studies on ultrafast radiationless decay. Since 2008 a few theoretical groups have suggested significant contributions of other dark states S$<em>3$ ($^1$A$</em>\mathrm{u}$, n$\pi<sup>*$) and S$<em>4$ ($^1$B$</em>{2\mathrm{g}}$, n$\pi<sup>*$) to the decay of S$_2$. We have previously reported the results of nuclear wave packet simulations [Phys. Chem. Chem. Phys. 17, 2012 (2015)] and photoelectron spectrum calculations [Chem. Phys. 515, 704 (2018)] that support the conventional two-state picture. In this article, the two different approaches, i.e., wave packet simulation and photoelectron spectrum calculation are combined: We computed the time-resolved vacuum ultraviolet photoelectron spectrum and photoelectron angular distribution for the ionization of the wave packet transferred from S$_2$ to S$_1$. The present results reproduce almost all the characteristic features of the corresponding experimental time-resolved spectrum [T. Horio et al., J. Chem. Phys. 145, 044306 (2016)] such as a rapid change from a three-band to two-band structure. This further supports the existence and character of the widely accepted pathway (S$_2$ $\rightarrow$ S$_1$) of ultrafast internal conversion in pyrazine.