Non-adiabatic transition probability dependence on conical intersection topography
File(s)malhado_hynes_2016.pdf (979.85 KB)
Accepted version
Author(s)
Malhado, JP
Hynes, JT
Type
Journal Article
Abstract
We derive a closed form analytical expression for the non-adiabatic transition probability for a distribution of trajectories passing through a generic conical intersection (CI), based on the Landau-Zener equation for the non-adiabatic transition probability for a single straight-line trajectory in the CI's vicinity. We investigate the non-adiabatic transition probability's variation with topographical features and find, for the same crossing velocity, no intrinsic difference in efficiency at promoting non-adiabatic decay between peaked and sloped CIs, a result in contrast to the commonly held view. Any increased efficiency of peaked over sloped CIs is thus due to dynamical effects rather than to any increased transition probability of topographical origin. It is also shown that the transition probability depends in general on the direction of approach to the CI, and that the coordinates' reduced mass can affect the transition probability via its influence on the CI topography in mass-scaled coordinates. The resulting predictions compare well with surface hopping simulation results.
Date Issued
2016-11-17
Date Acceptance
2016-10-25
Citation
Journal of Chemical Physics, 2016, 145 (19)
ISSN
1089-7690
Publisher
AIP Publishing
Journal / Book Title
Journal of Chemical Physics
Volume
145
Issue
19
Copyright Statement
© 2016 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in J. Chem. Phys. 145, 194104 (2016) and may be found at http://dx.doi.org/10.1063/1.4967259
Identifier
http://www.ncbi.nlm.nih.gov/pubmed/27875884
Subjects
Chemical Physics
02 Physical Sciences
03 Chemical Sciences
09 Engineering
Publication Status
Published
Coverage Spatial
United States
Article Number
194104