Author:
Hippler H.,Olzmann Matthias,Schalk O.,Unterreiner A.-N.
Abstract
Abstract
Internal conversion processes of 1,3,5-cycloheptatriene (CHT) and its perdeuterated counterpart (CHT-d8) in liquid cyclohexane have been studied by performing pump–probe experiments. The excitation and probe wavelength were 263 nm and 395 nm, respectively; the time resolution was 50 fs. Temporal absorption and transient anisotropy profiles were monitored. The experimental findings are consistent with the following mechanism: After excitation, the system undergoes a fast internal conversion associated with a molecular reorientation. The characteristic times are (110±10) fs for CHT and (150±20) fs for CHT-d8. The transient anisotropy as well as the isotope effect are consistent with a [1,7] hydrogen shift as reorientation mechanism. Moreover, initial anisotropies indicate that coherence effects between two excited states at early times may occur.
Subject
Physical and Theoretical Chemistry
Cited by
6 articles.
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