Ultrafast non-adiabatic dynamics of methyl substituted ethylenes : the π3s Rydberg state

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DOIResolve DOI: http://doi.org/10.1063/1.3652966
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TypeArticle
Journal titleJournal of Chemical Physics
Volume135
Issue16
Pages164309-1164309-10; # of pages: 10
AbstractExcited state unimolecular reactions of some polyenes exhibit localization of their dynamics at a single ethylenic double bond. Here we present studies of the fundamental photophysical processes in the ethylene unit itself. Combined femtosecond time-resolved photoelectron spectroscopy (TRPES) and ab initio quantum chemical calculations was applied to the study of excited state dynamics in cis-butene, trans-butene, trimethylethylene, and tetramethylethylene, following initial excitation to their respective π3s Rydberg states. The wavelength dependence of the π3s Rydberg state dynamics of tetramethylethylene was investigated in more detail. The π3s Rydberg to ππ* valence state decay rate varies greatly with substituent: the 1,2-di- and tri-methyl substituted ethylenes (cis-butene, trans-butene, and trimethylethylene) show an ultrafast decay (∼20 fs), whereas the fully methylated tetramethylethylene shows a decay rate of 2 to 4 orders of magnitude slower. These observations are rationalized in terms of topographical trends in the relevant potential energy surfaces, as found from ab initio calculations: (1) the barrier between the π3s state and the ππ* state increases with increasing methylation, and (2) the π3s/ππ* minimum energy conical intersection displaces monotonically away from the π3s Franck-Condon region with increasing methylation. The use of systematic methylation in combination with TRPES and ab initio computation is emerging as an important tool in discerning the excited state dynamics of unsaturated hydrocarbons.
Publication date
LanguageEnglish
AffiliationNRC Steacie Institute for Molecular Sciences; National Research Council Canada
Peer reviewedYes
NPARC number19739659
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Record identifier823fc35c-ee89-4c02-9cfb-c492c7feb199
Record created2012-04-02
Record modified2017-03-23
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