A test of RRKM theory against numerical simulation for classical chain molecules. II. Decomposition and vibrational relaxation in uniform chains |
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| Affiliation: | 1. NASA/Goddard Institute for Space Studies and Department of Applied Physics and Applied Mathematics, Columbia University, 2880 Broadway, New York, NY 10025, USA;2. Institut des Sciences Moléculaires d''Orsay (ISMO), CNRS, Université Paris-Saclay, Bât. 520, Campus d''Orsay 91405, Orsay-Cedex, France;1. Laboratoire de Météorologie Dynamique, IPSL, Sorbonne Université, ENS, Université PSL, École polytechnique, Institut Polytechnique de Paris, CNRS, Paris, France;2. Université de Tunis, Laboratoire de Spectroscopie et Dynamique Moléculaire, Ecole Nationale Supérieure d''Ingénieurs de Tunis, 5 Av. Taha Hussein, 1008 Tunis, Tunisia;3. Faculty of Physics, Hanoi National University of Education, 136 Xuan Thuy, Cau Giay, Hanoi, Vietnam |
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| Abstract: | Deviations from RRKM predictions for the fragmentation of a one-dimensional chain molecule are here studied in detail by numerical simulation and related to the rate of the vibrational relaxation. A measure of the degree of completion of vibrational relaxation is constructed, and its time development followed and compared with the progress of the reaction. The vibrational relaxation is initially rapid but then slows down as the reaction depletes the ensemble of rapidly relaxing trajectories. The observed decay rate starts from the RRKM value and then typically exceeds it at intermediate times crossing over to fall below the RRKM prediction at long times. |
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