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KINEMATIC CONSTRAINTS IN REACTIVE COLLISIONS
被引:28
作者:
SCHECHTER, I
LEVINE, RD
GORDON, RG
机构:
[1] HEBREW UNIV JERUSALEM,FRITZ HABER RES CTR MOLEC DYNAM,IL-91904 JERUSALEM,ISRAEL
[2] HARVARD UNIV,DEPT CHEM,CAMBRIDGE,MA 02138
关键词:
D O I:
10.1021/j100174a034
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 conversion of reactant orbital angular momentum to product rotational angular momentum is usually discussed for heavy + heavy-light A + BC reactive collisions. We argue that this will often be largely the case also for other mass combinations due to the steric requirements of the reaction. In particular, collinearly dominated reactions (e.g., H + H-2) would exhibit considerable kinematic polarization of the products. Computational results are provided for a number of reactive collisions (H + H-2, O + HCl, H + O2, Li + HF), where due to the stereochemistry, the kinematic effects can be different from those due to the mass change alone. The implications of the discussion are that (i) for collinearly dominated reactions, the reaction probability (the "opacity function") can be related to the measured product rotational state distribution, (ii) the kinematic polarization of the reaction products can be more extreme than is often recognized, and (iii) surprisal analysis of product rotation can be understood in terms of kinematic constraints.
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页码:8201 / 8205
页数:5
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