ENERGY-DEPENDENCE OF (DELTA-E)(DOWN) AND THE SHAPE OF FALLOFF CURVES - IMPLICATIONS FOR MODELING OF EXPERIMENTAL-DATA

被引:17
作者
KNYAZEV, VD
机构
[1] Department of Chemistry, Catholic University of America, Washington
关键词
D O I
10.1021/j100040a023
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The influence of the energy dependence of [Delta E](down) on the shape of falloff curves in unimolecular reactions is investigated using two model systems: the decomposition of C2H5 and the isomerization of cycloheptatriene (CHT). An exponential-down model of collisional energy transfer is used with [Delta E](down)(E) proportional to E(i), where i = 1 for the C2H5 decomposition and i = 1/2 for the CHT isomerization. It is demonstrated that neglect of the energy dependence of [Delta E](down) in the fitting of experimental falloff data may yield significant discrepancies between low-pressure and high-pressure results.
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页码:14738 / 14741
页数:4
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