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Constructive and Destructive Interference in Nonadiabatic Tunneling via Conical Intersections.
Changjian Xie1, Brian K Kendrick2, David R Yarkony3
1Department of Chemistry and Chemical Biology, University of New Mexico , Albuquerque, New Mexico 87131, United States.
Journal of Chemical Theory and Computation
|April 1, 2017
Summary
The geometric phase (GP) influences molecular dissociation near conical intersections (CIs) by causing constructive or destructive interference in tunneling wave functions, affecting dissociation rates. Including diagonal Born-Oppenheimer corrections is crucial for accurate results.
Area of Science:
- Quantum Chemistry
- Chemical Physics
- Molecular Dynamics
Background:
- Tunneling-facilitated dissociation near conical intersections (CIs) is a key process in molecular reactions.
- The molecular Aharonov-Bohm effect highlights the importance of geometric phase (GP) in ensuring single-valued wave functions around CIs.
Purpose of the Study:
- To investigate the impact of geometric phase (GP) on tunneling wave functions and lifetimes.
- To analyze the interference patterns induced by GP in vibrational states during dissociation.
- To evaluate the necessity of diagonal Born-Oppenheimer corrections for accurate modeling.
Main Methods:
- Development and analysis of a simplified two-dimensional model.
- Simulation of tunneling wave functions and their interference patterns.
- Inclusion and assessment of diagonal Born-Oppenheimer corrections.
Main Results:
- Geometric phase (GP) causes destructive interference for even quanta in the coupling mode and constructive interference for odd quanta.
- These interference patterns significantly influence molecular tunneling lifetimes.
- Diagonal Born-Oppenheimer corrections are essential for achieving agreement with exact computational results.
Conclusions:
- Geometric phase plays a critical role in modulating tunneling dynamics at conical intersections.
- The quantum interference effects are directly observable in tunneling wave functions and lifetimes.
- Accurate theoretical descriptions necessitate the inclusion of both geometric phase and diagonal Born-Oppenheimer corrections.