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"Pump–Probe Spectroscopy of Cycloheptatriene:
Transient Anisotropy and Isotope Effect" H. Hippler, M. Olzmann, O. Schalk, A.-N. UnterreinerZ. Phys. Chem., 219, 389 (2005). 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. This publication has not been written at BMO BMO authors (in alphabetic order): Oliver Schalk  WWW-Version |