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Dynamical stereochemistry of the hydrogen exchange reaction: A computational study
Author(s) -
Schechter I.,
Levine R. D.
Publication year - 1986
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550180911
Subject(s) - chemistry , excitation , reagent , hydrogen atom , branching (polymer chemistry) , reaction dynamics , computational chemistry , reactivity (psychology) , product (mathematics) , molecule , hydrogen , representation (politics) , computation , chemical physics , trajectory , molecular physics , atomic physics , quantum mechanics , physics , geometry , group (periodic table) , organic chemistry , mathematics , pathology , algorithm , politics , political science , computer science , law , medicine , alternative medicine
The barrier for the hydrogen exchange reaction increases with the bend angle of H 3 . The implications for the dynamics of the reaction are explored on two levels. The static one uses the concept of a relaxed potential. This provides for a convenient, yet realistic representation. Itallows for the response of the molecule to the approaching atom. Among features made very evident by the relaxed potential is the possibility that hotH atoms can react by insertion. It also shows the widening of the cone of acceptance upon reagent vibrational excitation. On the dynamical level, classical trajectory computations are used to illustrate the dependence of the reactivity on the angle of attack and on the translational and vibrational excitation of the reagents. Detailed product distributions are generally not sensitive to the attack angle. An exception is the HD/H 2 branching ratio in H + HD reactive collisions.