Impact of extended π conjugation on methyl rotor-induced IVR in aromatic molecules

Biswas, Partha ; Panja, Sujit S. ; Manogaran, S. ; Chakraborty, Tapas (2005) Impact of extended π conjugation on methyl rotor-induced IVR in aromatic molecules Journal of Physical Chemistry A, 109 (14). pp. 3225-3234. ISSN 1089-5639

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Laser-induced fluorescence excitation and resolved fluorescence spectra following excitations of the single vibronic levels (SVL) of p-vinyltoluene (p-VT) and p-vinylfluorobenzene (p-VFB) have been measured in a seeded supersonic free-jet expansion. A complete vibronic assignment of the fluorescence spectrum measured following excitation of the O00-band of p-VT has been presented. Normal vibrational modes in the S0 and S1 states of the molecule have been calculated by CASSCF method, and the correlation between the two set of modes is made by expressing the excited-state normal modes in terms of those of the ground state. The calculations predict that in the excited state methyl and vinyl torsional motions of p-VT are extensively mixed with many of the out-of-plane modes of the aromatic ring. Our resolved fluorescence spectral data measured following SVL excitations essentially agree with such predictions. In the excited state, the molecule exhibits a dramatically low threshold for the rotor-induced IVR in a supersonic jet expansion. Several mechanisms have been discussed to explain the phenomenon.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:100551
Deposited On:06 Dec 2016 12:17
Last Modified:06 Dec 2016 12:17

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