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化学学报
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化学学报 ›› 1997, Vol. 55 ›› Issue (5): 448-452. 上一篇    下一篇

研究论文

H2O(HOD) + Cl→HCl(DCl) + OH(OD)反应动态学的理论研究

曹晓燕;李宗和;刘若庄   

  1. 北京师范大学化学系
  • 发布日期:1997-05-15

Theoretical studies on reaction dynamics of H2O(HOD) + Cl→HCl(DCl) + OH(OD)

CAO XIAOYAN;LI ZONGHE;LIU RUOZHUANG   

  • Published:1997-05-15

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467

被引次数

2

用从头算方法, 获得了H2O + Cl→HCl + OH(R1), HOD +Cl→DCl + OH(R2), HOD + Cl→HCl + OD(R3)反应的内禀反应坐标(IRC)。根据传统过渡态、变分过渡态理论及相应的隧道效应校正, 计算了反应的速率常数。对已有实验速率常数值的R1反应, 我们计算的结果和实验一致。根据Truhlar的振动选态公式, 分别讨论了激发HOD中OH, OD振动模式对反应速率的影响,得到激发HOD中的OH振动模式将有利于产物OD + HCl生成, 和实验的结论相一致。

关键词: 氯, 重水, 从头计算法, 反应速度常数, 过渡态理论

Based on ab initio methods with gradient technique, the intrinsic reaction coordinate (IRC) of the reactions H2O + Cl→HCl + OH(R1), HOD + Cl→DCl + OH(R2) and HOD + Cl→HCl + OD(R3) are traced by using numerical method. The theoretical rate constants for the R1-R3 reactions are calculated by the conventional transition-state theory, variational transition-state theory and semiclassical vibrationally adiabatic transmission coefficients. The calculated rate constants for the R1 reaction are in good agreement with the experimental results. The state-selected reaction rate constants for the R2, R3 reactions are also calculated. It is concluded that the excitation of reactant HOD (nOH=1) is beneficial to the production of product HCl + OD. Theis result agrees with experiment.

Key words: CHLORINE, HEAVY WATER, AB INITIO CALCULATION, REACTION RATE CONSTANT, TRANSITION STATE THEORY

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