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Analytical solution of vibrational–rotational energy transfer in the dissociation and relaxation of N 2 , Br 2 , and CO at high temperature
Author(s) -
Forst Wendell
Publication year - 1981
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.550130904
Subject(s) - chemistry , dissociation (chemistry) , vibrational energy relaxation , diatomic molecule , rotational energy , atomic physics , argon , excited state , exponential function , relaxation (psychology) , degrees of freedom (physics and chemistry) , vibrational energy , thermodynamics , molecule , physics , psychology , mathematical analysis , social psychology , mathematics , organic chemistry
An approximate analytical solution of relaxation in a low‐pressure system with exponential transition probabilities is given for vibrational–rotational energy transfer in the dissociation of diatomics. The main assumption is that the rotational degrees of freedom are in thermal equilibrium at all times, and that the barrier to dissociation in the vibrational–rotational plane is linear and asymmetric. The theory is applied to high‐temperature dissociations of N 2 , Br 2 , and CO in excess argon, with satisfactory agreement with available experimental data.