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OH+HCl→Cl+H2O反应中的反应物转动激发效应.

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本文在最近构建的F12a势能面上,对OH+HCl→Cl+H2O的一系列反应物转动激发态进行了势能平均的五维含时波包计算,得到了初始态选择的反应几率和速率常数.研究发现,除了很低碰撞能量,单独激发反应物HCl到j1=2或者OH到j2=1得到了总反应几率的最大值.在低能区域,随着OH转动激发的增加,反应几率的共振增强迅速减小,导致250 K以下的速率常数迅速下降.HCl和OH同时转动激发的速率常数不是单独激发结果的简单叠加.最后,通过对(5,5)态以下初始转动态的速率常数进行玻尔兹曼平均,得到了反应的热速率常数,与实验结果基本吻合.
Effects of Reagent Rotational Excitation on OH+HCl→Cl+H2O Reaction
Potential-averaged five-dimensional(PA5D)time-dependent wave packet calculations have been carried out to ob-tain the initial state-specific reaction proba-bilities and rate con-stants for a series of reactant rotationally excited states of the title reaction on one of our re-cently developed potential energy surface(F12a PES).It is found that individual excitation of the reactant HCl to j1=2 or OH to j2=1 yields the largest total reaction probability except for low collision energies.In the low energy region,the resonance enhancement of reaction proba-bility decreases rapidly with the increase of OH rotational excitation,resulting in a rapid de-cline in the rate constant below 250 K.The rate constant of the simultaneous HCl and OH ro-tational excitation is not a simple superposition of the results of the separate excitation.Fi-nally,we obtain the thermal rate constants of the reaction by Boltzmann averaging the rate constants for initial rotational states up to(5,5),which are in reasonable agreement with the experimental results.

Reagent rotational excitationTime-dependent wave packetReaction probabil-ityFeshbach resonanceRate constant

徐昕、陈俊、刘舒、张东辉

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中国科学院大连化学物理研究所,分子反应动力学国家重点实验室,大连 116023

中国科学院大学,北京 100049

中国科学院福建物质结构研究所,结构化学国家重点实验室,福州 350002

反应物转动激发 含时波包 反应几率 Feshbach共振 速率常数

国家自然科学基金国家自然科学基金国家自然科学基金Innovation Program for Quantum Science and Technology中国科学院战略规划重点项目Liaoning Revitalization Talents ProgramDalian Innovation Support Program

2227310422022306222882012021ZD 0303305XDB0450202XLYC22030622021RD05

2024

10.1063/1674-0068/cjcp2401003

化学物理学报(英文版)
中国物理学会

化学物理学报(英文版)

CSTPCDEI
影响因子：0.162
ISSN：1674-0068
年,卷(期)：2024.37(2)
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