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J Chem Phys. 2011 May 14;134(18):184313. doi: 10.1063/1.3586809.

Time-resolved photoelectron imaging of S2 → S1 internal conversion in benzene and toluene.

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1
Japan Science and Technology Agency, CREST, Sanbancho, Chiyoda-ku, Tokyo, Japan.

Abstract

Ultrafast internal conversion of benzene and toluene from the S(2) states was studied by time-resolved photoelectron imaging with a time resolution of 22 fs. Time-energy maps of the photoelectron intensity and the angular anisotropy were generated from a series of photoelectron images. The photoelectron kinetic energy distribution exhibits a rapid energy shift and intensity revival, which indicates nuclear motion on the S(2) adiabatic surface, while the ultrafast evolution of the angular anisotropy revealed a change in the electronic character of the S(2) adiabatic surface. From their decay profiles of the total photoelectron intensity, the time constants of 48 ± 4 and 62 ± 4 fs were determined for the population decay from the S(2) states in benzene and toluene, respectively.

PMID:
21568512
DOI:
10.1063/1.3586809
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