Imperial College London
Dr João Pedro Malhado

DrJoão PedroMalhado

Faculty of Natural Sciences, Department of Chemistry

Senior Teaching Fellow
 
 
 
//

Contact

 

malhado

 
 
//

Location

 

248ChemistrySouth Kensington Campus

//

Summary

 

Publications

Citation

BibTex format

@article{Malhado:2016:10.1063/1.4967259,
author = {Malhado, JP and Hynes, JT},
doi = {10.1063/1.4967259},
journal = {Journal of Chemical Physics},
title = {Non-adiabatic transition probability dependence on conical intersection topography},
url = {http://dx.doi.org/10.1063/1.4967259},
volume = {145},
year = {2016}
}
Download

RIS format (EndNote, RefMan)

TY  - JOUR
AB  - 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.
AU  - Malhado,JP
AU  - Hynes,JT
DO  - 10.1063/1.4967259
PY  - 2016///
SN  - 1089-7690
TI  - Non-adiabatic transition probability dependence on conical intersection topography
T2  - Journal of Chemical Physics
UR  - http://dx.doi.org/10.1063/1.4967259
UR  - http://www.ncbi.nlm.nih.gov/pubmed/27875884
UR  - http://hdl.handle.net/10044/1/43047
VL  - 145
ER  -
Download