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Journal of Physical Chemistry A, Vol.102, No.46, 9101-9105, 1998
Independent determination of supercollision energy loss magnitudes and rates in highly vibrationally excited pyrazine with E-vib = 36000-41000 cm(-1)
We report results of the first state-resolved study of large Delta E energy transfer resulting from collisions of highly excited pyrazine with initial vibrational energies of 36000-41000 cm(-1). We have used transient infrared absorption spectroscopy to monitor the rotational and translational energy gain in a CO2 bath at short times following collisions with highly excited pyrazine. We have measured nascent distributions of high-energy rotational states, J =56-84, for CO2 in its ground vibrationless (00(0)0) state, the translational energy gain associated with these excited rotational states, and state-resolved rate constants for excitation of the high-energy bath states. Our results show that for the CO2 rotational states investigated, the nascent rotational distributions and translational energies change very little for a 13% change in pyrazine energy. In contrast, the rate constants for these events are strongly influenced by the donor internal energy content and increase by an order of magnitude for a 5000 cm(-1) increase in pyrazine vibrational energy. Our state- and energy-resolved results are compared with experimental measurements of [Delta E], and implications for the energy dependence of the probability distribution function are discussed.
Keywords:COLLISIONAL DEACTIVATION, MULTIPHOTON IONIZATION, T1 PYRAZINE;WALK MODEL, RELAXATION, MOLECULES, STATE, DEPENDENCE, BENZENE;AZULENE