Role of Rydberg states in the photochemical dynamics of ethylene

Toshifumi Mori, William J. Glover, Michael S. Schuurman, Todd J. Martinez

Research output: Contribution to journalArticlepeer-review

112 Citations (Scopus)

Abstract

We use the ab initio multiple spawning method with potential energy surfaces and nonadiabatic coupling vectors computed from multistate multireference perturbation theory (MSPT2) to follow the dynamics of ethylene after photoexcitation. We introduce an analytic formulation for the nonadiabatic coupling vector in the context of MSPT2 calculations. We explicitly include the low-lying 3s Rydberg state which has been neglected in previous ab initio molecular dynamics studies of this process. We find that although the 3s Rydberg state lies below the optically bright ππ* state, little population gets trapped on this state. Instead, the 3s Rydberg state is largely a spectator in the photodynamics, with little effect on the quenching mechanism or excited state lifetime. We predict the time-resolved photoelectron spectrum for ethylene and point out the signature of Rydberg state involvement that should be easily observed.

Original languageEnglish
Pages (from-to)2808-2818
Number of pages11
JournalJournal of Physical Chemistry A
Volume116
Issue number11
DOIs
Publication statusPublished - Mar 22 2012
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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