$S_{1}-S_{0}$ VIBRONIC SPECTRA OF BENZENE CLUSTERS REVISITED: II. THE TRIMER
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Date
2001
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Ohio State University
Abstract
As the second part of our recent reinvestigation on the electronic spectra of benzene $clusters,^{a}$ we present the trimer vibronic system studied by two-color (2C) resonance enhanced two-photon ionization (R2PI) and UV-UV holeburing experiments. This band system is observed only in the dimer-ion channel even with 2C-R2PI because of extensive fragmentation after photoionization, and thus it has been incorrectly assigned to an isomeric form of the $dimer.^{b}$ Detailed examination with mixed samples of $C_{6}H_{6}$ and $C_{6}D_{6}$ has revealed that the parent neutral has a single isomeric form for each isotopomer, $(C_{6}H_{6})_{m}(C_{6}D_{6})_{n}$ with $m + n = 3$. This observation confirms the equivalency in three benzene sites, which is consistent with the most stable cyclic form predicted by a NEMO $calculation.^{c}$ One of the intermolecular modes shows prominent Franck-Condon activity, implying a substantial conformational change via photoexcitation. Other details observed in the vibrionc spectra, e.g., exitonic splitting, will also be discussed.
Description
$^{a}$T. Iimori and Y. Ohshima, J. Chem. Phys. 114, 2867 (2001). $^{b}$W. Scherzer, O. Kratzschmar, H. L. Selzle, and E. W. Schlag, Z. Naturforsch. 47a, 1248 (1992). $^{c}$O. Engkvist, P. Hobza, H. L. Selzle, and E. W. Schlag, J. Chem. Phys. 110, 5758 (1999).
Author Institution: Graduate School of Science, Kyoto University; Department of Chemistry, Graduate School of Science, Kyoto University
Author Institution: Graduate School of Science, Kyoto University; Department of Chemistry, Graduate School of Science, Kyoto University