4.8 Article

Nonadiabatic Couplings Can Speed Up Quantum Tunneling Transition Path Times

期刊

JOURNAL OF PHYSICAL CHEMISTRY LETTERS
卷 13, 期 45, 页码 10558-10566

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.2c03008

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资金

  1. Israel Science Foundation
  2. [408/19]
  3. [2965/19]

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The study shows that nonadiabatic couplings can speed up tunneling events in nonadiabatic systems, and the appropriate measure to determine tunneling flight time is the Wigner phase time.
Quantum tunneling is known to play an important role in the dynamics of systems with nonadiabatic couplings. However, until recently, the time-domain properties of nonadiabatic scattering have been severely under-explored. Using numerically exact quantum methods, we study the impact that nonadiabatic couplings have on the time it takes to tunnel through a barrier. We find that the Wigner phase time is the appropriate measure to use when determining the tunneling flight time also when considering nonadiabatic systems. The central result of the present study is that in an avoided crossing system in one dimension, the nonadiabatic couplings speed up the tunneling event, relative to the adiabatic case in which all nonadiabatic coupling is ignored. This has implications for both the study of quantum tunneling times and for the field of nonadiabatic scattering and chemistry.

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