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

Manabu Kanno, Benoît Mignolet, Françoise Remacle, Hirohiko Kono

Research output: Contribution to journalArticlepeer-review

Abstract

The internal conversion from the optically bright S2 (1B2u, ππ*) state to the dark S1 (1B3u, nπ*) 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 S3 (1Au, nπ*) and S4 (1B2g, nπ*) to the decay of S2. We have previously reported the results of nuclear wave packet simulations [Kanno et al., Phys. Chem. Chem. Phys. 17, 2012 (2015)] and photoelectron spectrum calculations [Mignolet et al., 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 S2 to S1. The present results reproduce almost all the characteristic features of the corresponding experimental time-resolved spectrum [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 (S2 → S1) of ultrafast internal conversion in pyrazine.

Original languageEnglish
Article number224304
JournalJournal of Chemical Physics
Volume154
Issue number22
DOIs
Publication statusPublished - 2021 Jun 14

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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