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Title: Constructive and Destructive Interference in Nonadiabatic Tunneling via Conical Intersections

As a manifestation of the molecular Aharonov–Bohm effect, tunneling-facilitated dissociation under a conical intersection (CI) requires the inclusion of the geometric phase (GP) to ensure a single-valued adiabatic wave function encircling the CI. Here, we demonstrate using a simple two-dimensional model that the GP induces destructive interference for vibrational states with even quanta in the coupling mode, but it leads to constructive interference for those with odd quanta. The interference patterns are manifested in tunneling wave functions and clearly affect the tunneling lifetime. Furthermore, we show that the inclusion of the diagonal Born–Oppenheimer correction is necessary for agreement with exact results.
Authors:
 [1] ;  [2] ;  [3] ; ORCiD logo [1]
  1. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemistry and Chemical Biology
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Theoretical Division
  3. Johns Hopkins Univ., Baltimore, MD (United States). Dept. of Chemistry
Publication Date:
Report Number(s):
LA-UR-17-20533
Journal ID: ISSN 1549-9618; AC52-06NA25396
Grant/Contract Number:
SC0015997; AC52-06NA25396; CHE-1361121; 20170221ER
Type:
Published Article
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 13; Journal Issue: 5; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Research Org:
Univ. of New Mexico, Albuquerque, NM (United States); Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and Physical Chemistry
OSTI Identifier:
1349949
Alternate Identifier(s):
OSTI ID: 1361506; OSTI ID: 1414100