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Title: Nonadiabatic tunneling via conical intersections and the role of the geometric phase

Journal Article · · Physical Review A
 [1];  [2];  [1]
  1. Univ. of New Mexico, Albuquerque, NM (United States)
  2. Johns Hopkins Univ., Baltimore, MD (United States)
+ Show Author Affiliations

As a ubiquitous quantum effect, tunneling has attracted attention ever since the dawn of quantum mechanics. However, recent evidence suggests that nonadiabatic atomic tunneling near a conical intersection (CI) behaves differently from its adiabatic counterpart, producing lifetime differences of up to two orders of magnitude. Using two-dimensional models, we demonstrate here that the failure of the adiabatic model in describing tunneling near a CI can be attributed largely to the neglect of the geometric phase, which is associated with the adiabatic electronic wave function transported around a CI. Furthermore, the geometric phase–induced destructive interference among wave functions following different paths around the CI, manifested as a node in the adiabatic wave function, retards tunneling.

Research Organization:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC)
Grant/Contract Number:
SC0015997
OSTI ID:
1535725
Alternate ID(s):
OSTI ID: 1342804
Journal Information:
Physical Review A, Vol. 95, Issue 2; ISSN 2469-9926
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 46 works
Citation information provided by
Web of Science

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Cited By (10)

Photodissociation of phenol in the adiabatic representation: Tunneling, motions of phenyl ring, and kinetic isotope effects journal September 2018
Intrinsic and light-induced nonadiabatic phenomena in the NaI molecule journal January 2017
Diabatic states, nonadiabatic coupling, and the counterpoise procedure for weakly interacting open-shell molecules journal March 2018
Non-adiabatic quantum reactive scattering in hyperspherical coordinates journal January 2018
Geometric phase effects on photodissociation dynamics of diatomics journal December 2018
A discontinuous basis enables numerically exact solution of the Schrödinger equation around conical intersections in the adiabatic representation journal February 2019
Vibronic coupling in the F·CH 4 prereactive complex journal September 2019
Triplet vs πσ* state mediated N–H dissociation of aniline journal October 2019
Continuous vibronic symmetries in Jahn–Teller models journal July 2018
Interplay of electron-phonon nonadiabaticity and Raman scattering in the wavepacket dynamics of electron-phonon-photon systems journal June 2019

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