The role of Rydberg states in the photochemical dynamics of ethylene

Download
  1. (PDF, 2 MB)
  2. Get@NRC: The role of Rydberg states in the photochemical dynamics of ethylene (Opens in a new window)
DOIResolve DOI: http://doi.org/10.1021/jp2097185
AuthorSearch for: ; Search for: ; Search for: ; Search for:
TypeArticle
Journal titleJournal of Physical Chemistry A
Volume116
Issue11
Pages28082818; # of pages: 11
AbstractWe 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.
Publication date
LanguageEnglish
AffiliationNRC Steacie Institute for Molecular Sciences; National Research Council Canada
Peer reviewedYes
NPARC number19734688
Export citationExport as RIS
Report a correctionReport a correction
Record identifiercc2e75b2-0263-4f14-9908-cafe2f59e8d6
Record created2012-03-29
Record modified2016-05-09
Bookmark and share
  • Share this page with Facebook (Opens in a new window)
  • Share this page with Twitter (Opens in a new window)
  • Share this page with Google+ (Opens in a new window)
  • Share this page with Delicious (Opens in a new window)