✍ Scribed by Li-Ping Ju; Ke-Li Han; John Z. H. Zhang
No coin nor oath required. For personal study only.
In this review article, we present a systematic comparison of the theoretical rate constants for a range of bimolecular reactions that are calculated by using three different classes of theoretical methods: quantum dynamics (QD), quasi‐classical trajectory (QCT), and transition state theory (TST) approaches. The study shows that the difference of rate constants between TST results and those of the global dynamics methods (QD and QCT) are seen to be related to a number of factors including the number of degrees‐of‐freedom (DOF), the density of states at transition state (TS), etc. For reactions with more DOF and higher density of states at the TS, it is found that the rate constants from TST calculations are systematically higher than those obtained from global dynamics calculations, indicating large recrossing effect for these systems. The physical insight of this phenomenon is elucidated in the present review. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2009
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The following gas-phase reactions: (1) ( 2 ) were studied by the competitive method with CF,I as the source of radicals. The kinetic parameters obtained in the temperature range 533-613 K and 503-613 K respectively for chlorine atom transfer reactions are given by: log hl/h,"(cm3 mol-" s -") = 16