期刊
JOURNAL OF PHYSICAL CHEMISTRY B
卷 125, 期 22, 页码 5959-5970出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcb.1c02851
关键词
-
资金
- NSFC [21673246, 21933011]
- Beijing Municipal Science & Technology Commission [Z191100007219009]
- K. C. Wong Education Foundation
This study utilized the numerically exact hierarchical equations of motion (HEOM) method to investigate hydrogen and deuterium transfer reactions in condensed phases, revealing diverse mechanisms controlling the behaviors in different tunneling reaction scenarios. The results can help validate the effectiveness of various approximate methods in studying tunneling effects.
In recent years, many experiments have shown large kinetic isotope effects (KIEs) for hydrogen transfer reactions in condensed phases as evidence of strong quantum tunneling effects. Since accurate calculation of the tunneling dynamics in such systems still present significant challenges, previous studies have employed different types of approximations to estimate the tunneling effects and KIEs. In this work, by employing model systems consisting of a double-well coupled to a harmonic bath, we calculate the tunneling effects and KIEs using the numerically exact hierarchical equations of motion (HEOM) method. It is found that hydrogen and deuterium transfer reactions in the same system may show rather different behaviors, where hydrogen transfer is dominated by tunneling between the two lowest vibrational states and deuterium transfer is controlled by excited vibrational states close to the barrier top. The simulation results are also used to test the validity of various approximate methods. It is shown that the Wolynes theory of dissipative tunneling gives a good estimation of rate constants in the over-the-barrier regime, while the nonadiabatic reaction rate theory based on the Landau-Zener formula is more suitable for deep tunneling reactions.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据