PMID- 34033714
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20210610
IS  - 1520-5207 (Electronic)
IS  - 1520-5207 (Linking)
VI  - 125
IP  - 22
DP  - 2021 Jun 10
TI  - Understanding the Large Kinetic Isotope Effect of Hydrogen Tunneling in Condensed 
      Phases by Using Double-Well Model Systems.
PG  - 5959-5970
LID - 10.1021/acs.jpcb.1c02851 [doi]
AB  - 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.
FAU - Liu, Yanying
AU  - Liu Y
AD  - Beijing National Laboratory for Molecular Sciences, State Key Laboratory for 
      Structural Chemistry of Unstable and Stable Species, CAS Research/Education 
      Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese 
      Academy of Sciences, Zhongguancun, Beijing 100190, China.
AD  - University of Chinese Academy of Sciences, Beijing 100049, China.
AD  - Physical Science Laboratory, Huairou National Comprehensive Science Center, 
      Beijing 101407, China.
FAU - Yan, Yaming
AU  - Yan Y
AD  - Beijing National Laboratory for Molecular Sciences, State Key Laboratory for 
      Structural Chemistry of Unstable and Stable Species, CAS Research/Education 
      Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese 
      Academy of Sciences, Zhongguancun, Beijing 100190, China.
AD  - University of Chinese Academy of Sciences, Beijing 100049, China.
AD  - Physical Science Laboratory, Huairou National Comprehensive Science Center, 
      Beijing 101407, China.
FAU - Xing, Tao
AU  - Xing T
AD  - Beijing National Laboratory for Molecular Sciences, State Key Laboratory for 
      Structural Chemistry of Unstable and Stable Species, CAS Research/Education 
      Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese 
      Academy of Sciences, Zhongguancun, Beijing 100190, China.
AD  - University of Chinese Academy of Sciences, Beijing 100049, China.
AD  - Physical Science Laboratory, Huairou National Comprehensive Science Center, 
      Beijing 101407, China.
FAU - Shi, Qiang
AU  - Shi Q
AUID- ORCID: 0000-0002-9046-2924
AD  - Beijing National Laboratory for Molecular Sciences, State Key Laboratory for 
      Structural Chemistry of Unstable and Stable Species, CAS Research/Education 
      Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese 
      Academy of Sciences, Zhongguancun, Beijing 100190, China.
AD  - University of Chinese Academy of Sciences, Beijing 100049, China.
AD  - Physical Science Laboratory, Huairou National Comprehensive Science Center, 
      Beijing 101407, China.
LA  - eng
PT  - Journal Article
DEP - 20210525
PL  - United States
TA  - J Phys Chem B
JT  - The journal of physical chemistry. B
JID - 101157530
SB  - IM
EDAT- 2021/05/26 06:00
MHDA- 2021/05/26 06:01
CRDT- 2021/05/25 20:08
PHST- 2021/05/26 06:00 [pubmed]
PHST- 2021/05/26 06:01 [medline]
PHST- 2021/05/25 20:08 [entrez]
AID - 10.1021/acs.jpcb.1c02851 [doi]
PST - ppublish
SO  - J Phys Chem B. 2021 Jun 10;125(22):5959-5970. doi: 10.1021/acs.jpcb.1c02851. Epub 
      2021 May 25.