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Strong Acceleration of Chemical Reactions Occurring Through the Effects of Rotational Excitation on Collision Geometry
Author(s) -
Miklavc Adolf
Publication year - 2001
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/1439-7641(20010917)2:8/9<552::aid-cphc552>3.0.co;2-5
Subject(s) - excitation , acceleration , chemical reaction , chemistry , atomic physics , molecule , amplitude , chemical physics , molecular physics , physics , classical mechanics , optics , biochemistry , organic chemistry , quantum mechanics
Accelerating chemical reactions by rotational excitation increases both the energy available for barrier crossing and also changes the distribution of collisions with the barrier, as demonstrated herein on the gas‐phase reactions O+HCl(DCl)→OH(OD)+Cl. In the picture, the dependence of the barrier energy E b on the Jacobi angle γ is given, together with the distribution of collisions with the barrier at j =0 (▪) and 16 (▾). Such a mechanism should arise from large‐amplitude oscillatory motions of molecules or reacting atomic groups. It should thus occur also in condensed phases and it should lead to nonenergetic (nonthermal) acceleration of chemical reactions by microwaves.