ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Rates of intermolecular-to-intramolecular energy transfer and chemical reaction were determined by quantum mechanical calculations on systems of strongly interacting molecules at high shock pressure. The energy transfer rate was estimated by utilizing a theory of radiationless transitions which describes the coupling of a sparse set of internal mode energy levels with a quasicontinuum of intermolecular mode energy levels. An important quantity in this theory is the time tpv required for activation of the internal modes. Calculated values of tpv 〈 1 μsec are identified with the most efficient transfer of energy when the molecules interact and react bimolecularly in the head-to-tail configuration. These times are consistent with those found in shock experiments and those calculated by other techniques. A comparison of tpv with chemical reaction half-lives indicates that energy transfer and reaction alternate as rate-determining steps over large ranges of P and T.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560300740
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