Strong non-Arrhenius behavior at low temperatures in the OH + HCl → H(2)O + Cl reaction due to resonance induced quantum tunneling.
Strong non-Arrhenius behavior at low temperatures in the OH + HCl → H(2)O + Cl reaction due to resonance induced quantum tunneling.
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由于共振诱导的量子隧道效应，OH HCl → H2O Cl 反应在低温下表现出强烈的非阿伦尼乌斯行为
DOI：
10.1039/d2sc01958b
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发表时间：
2022-07-06
期刊：
影响因子：
8.4
通讯作者：
中科院分区：
文献类型：
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作者：
OH+HCl-→-H2O+Cl反应释放出氯原子，可催化平流层臭氧破坏反应。测量的反应速率系数在低温下大大偏离阿累尼乌斯极限，并在T<；250K时变得基本上与温度无关，显然是由于量子隧穿；然而，量子隧穿的性质尚不清楚。在这里，我们报道了两个新构造的势能面上的反应的随时间变化的波包研究。结果表明，由于氢键相互作用，OH+HCl反应在入射通道的弯曲/扭转激发的振动绝热势垒中具有许多Feshbach共振。这些共振态极大地诱导氢原子通过反应势垒的量子隧穿，导致实验观察到的反应速率在低温下与Arrhenius行为有很大偏离。OH+HCl反应在入射通道的氢键势垒中有许多Feshbach共振捕获，这大大提高了低温下的反应速率。
The OH + HCl → H2O + Cl reaction releases Cl atoms, which can catalyze the ozone destruction reaction in the stratosphere. The measured rate coefficients for the reaction deviate substantially from the Arrhenius limit at low temperatures and become essentially independent of temperature when T < 250 K, apparently due to quantum tunneling; however, the nature of the quantum tunneling is unknown. Here, we report a time-dependent wave packet study of the reactions on two newly constructed potential energy surfaces. It is found that the OH + HCl reaction possesses many Feshbach resonances trapped in a bending/torsion excited vibrational adiabatic potential well in the entrance channel due to hydrogen bond interaction. These resonance states greatly induce quantum tunneling of a hydrogen atom through the reaction barrier, causing the reaction rates to deviate substantially from Arrhenius behavior at low temperature, as observed experimentally. The OH + HCl reaction possesses many Feshbach resonances trapped in the hydrogen bond well in the entrance channel, which substantially enhance the reaction rates at low temperatures.
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影响因子：
2.9
作者：
Li, Jun;Jiang, Bin;Guo, Hua
通讯作者：
Guo, Hua
影响因子：
2.9
作者：
Menendez, M.;Jambrina, P. G.;Aoiz, F. J.
通讯作者：
Aoiz, F. J.
影响因子：
1.5
作者：
MOLINA, MJ;MOLINA, LT;SMITH, CA
通讯作者：
SMITH, CA
DOI：
10.1039/f29817701949
发表时间：
1981-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS II
影响因子：
--
作者：
HUSAIN, D;PLANE, JMC;SLATER, NKH
通讯作者：
SLATER, NKH
影响因子：
56.9
作者：
Kim, Jongjin B.;Weichman, Marissa L.;Manolopoulos, David E.
通讯作者：
Manolopoulos, David E.