Statistical theory of collisional energy transfer in molecular collisions. trans-stilbene deactivation by argon, carbon dioxide, and n-heptane

The Journal of Physical Chemistry. a
Daniel Nilsson, Sture Nordholm

Abstract

Recent advances in experimental techniques have made it possible to measure the full conditional probability density P(E, E') of the energy transfer between two colliding molecules in the gas phase, one of which is highly energized and the other in thermal equilibrium at a given temperature. Data have now become available for trans-stilbene deactivation by the three bath gas molecules Ar, CO2, and n-heptane (C7H16). The initial energies of trans-stilbene are set to 10 000, 20 000, 30 000, and 40 000 cm (-1). The results show that exceptionally large amounts of energy are transferred in each collision. By application of our partially ergodic collision theory (PECT), we find that the energy transfer efficiency betaE ranges from a rather normal value of 0.15 for n-heptane at the highest excitation energy to 0.93-nearly in the ergodic collision limit-for the argon bath gas at high excitation energy. Generally, the PECT produces a good fit of the data except for the nearly elastic peak in the case of n-heptane, where PECT produces a rounded and downshifted peak in contrast to a sharply defined elastic maximum of the monoexponential functional fit produced from the original experimental data obtained by kinetically controlled selecti...Continue Reading

Citations

Aug 25, 2015·The Journal of Physical Chemistry. a·Riccardo ConteJoel M Bowman
Aug 15, 2014·The Journal of Physical Chemistry. a·Riccardo ConteJoel M Bowman
Aug 15, 2014·The Journal of Physical Chemistry. a·Paul L HoustonJoel M Bowman
Apr 7, 2015·Chemical Reviews·Luc VereeckenMichael J Pilling
Apr 25, 2015·The Journal of Physical Chemistry. a·Paul L HoustonJoel M Bowman

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