On the distinction between weak and strong collisions in the theory of unimolecular reactions

Autor:	H. O. Pritchard
Rok vydání:	1988
Předmět:	Analytical expressions Methyl isocyanide Stereochemistry General Engineering Activation energy Cyclopropane chemistry.chemical_compound chemistry Chemical physics Intramolecular force Vibrational energy relaxation Molecule Physical and Theoretical Chemistry Isomerization
Zdroj:	The Journal of Physical Chemistry. 92:4333-4339
ISSN:	1541-5740 0022-3654
Popis:	Beginning with the conjecture that the principal difference between weakand strong-collision reactions is intrinsic to the reactant molecule, rather than in the nature of the collisions between molecules, a reanalysis of the unimolecular falloff phenomenon is given. The rate at which the molecule acquires energy to react is identified with the bulk vibrational relaxation rate, and the rate at which reactive molecules lose their energy of activation is taken to be the collisional deactivation rate, as used in existing theory; certain choices must be made for the rates of intramolecular vibrational relaxation (randomization) among the reactive states, with the result that the same analytic expression for the unimolecular rate can be made to reproduce the falloff shapes for such diverse reactant molecules as nitrous oxide, methyl isocyanide, and cyclopropane, as well as their correct positions on the pressure axis.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::e22b75ffdd08902114b66a87d1495396 https://doi.org/10.1021/j100326a019 Zobrazit plný text záznamu