Open AccessConstructive and Destructive Interference in Nonadiabatic Tunneling via Conical Intersections
Author(s) -
Changjian Xie,
Brian K. Kendrick,
David R. Yarkony,
Hua Guo
Publication year - 2017
Publication title -
journal of chemical theory and computation
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.001
H-Index - 185
eISSN - 1549-9626
pISSN - 1549-9618
DOI - 10.1021/acs.jctc.7b00124
Subject(s) - conical intersection , quantum tunnelling , adiabatic process , wave function , diagonal , geometric phase , conical surface , physics , interference (communication) , quantum mechanics , coupling (piping) , avoided crossing , constructive , dissociation (chemistry) , intersection (aeronautics) , wave packet , molecular physics , chemistry , molecule , computer science , materials science , channel (broadcasting) , telecommunications , mathematics , geometry , process (computing) , engineering , metallurgy , excited state , aerospace engineering , operating system
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. In this work, 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. It is further shown that the inclusion of the diagonal Born-Oppenheimer correction is necessary for agreement with exact results.