Abstract
We report on the study of intramolecular vibrational energy redistribution (IVR) in vibrationally cold anthracene and 9-cyanoanthracene. These molecules were expanded with argon from a pulsed linear nozzle and were excited by a tunable dye laser. IVR was probed mostly through the rotational and vibrational energy dependence of the resulting energy-resolved emission. The existence of vibrational mixing in the form of Fermi resonances is demonstrated. Large rotational effects were found and the energy-resolved emission was found to be very sensitive to the exact excitation wavelength of the exciting laser within the rotational contour. We have concluded that both anharmonic coupling and Coriolis coupling are important intrastate vibronic couplings. Intrastate IVR is shown to be associated with enhanced interstate electronic relaxation. The possible co-existence of Coriolis coupling and quantum beats in the time- and energy-resolved emission is discussed.
Published Version
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