THEORY OF THERMAL UNIMOLECULAR REACTIONS IN THE FALL-OFF RANGE .2. WEAK COLLISION RATE CONSTANTS

被引:563
作者
GILBERT, RG [1 ]
LUTHER, K [1 ]
TROE, J [1 ]
机构
[1] UNIV GOTTINGEN,INST PHYS CHEM,D-3400 GOTTINGEN,FED REP GER
来源
BERICHTE DER BUNSEN-GESELLSCHAFT-PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 1983年 / 87卷 / 02期
关键词
CHEMICAL REACTIONS - Reaction Kinetics;
D O I
10.1002/bbpc.19830870218
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 master equation of thermal unimolecular reactions in the fall-off range has been solved for a number of representative molecular systems. Weak collision broadening factors F**W**C(k// /k// infinity ) are derived and represented empirically. Weak collision efficiencies beta //c for the low pressure range are calculated for very high temperatures. Combined with earlier representations (part I) of strong collision broadening factors F**S**C(k//0/k// infinity ), compact empirical expressions for the rate coefficient in the full fall-off range are proposed. These expressions are useful for data representation and modeling of complex reaction system which involve isomerization, dissociation and recombination reactions.
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页码:169 / 177
页数:9
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