Imperial College London
Alternate

Professor Mike Robb, FRS

Faculty of Natural Sciences, Department of Chemistry

Chair in Chemistry
 
 
 
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Contact

 

+44 (0)20 7594 5757mike.robb Website

 
 
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Location

 

301cMolecular Sciences Research HubWhite City Campus

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Summary

 

Publications

Citation

BibTex format

@article{Robb:2015:10.1021/acs.jctc.5b00364,
author = {Robb, MA and Meisner, J and Vacher, M and Bearpark, M},
doi = {10.1021/acs.jctc.5b00364},
journal = {Journal of Chemical Theory and Computation},
pages = {3115--3122},
title = {Geometric rotation of the nuclear gradient at a conical intersection: Extension to complex rotation of diabatic states},
url = {http://dx.doi.org/10.1021/acs.jctc.5b00364},
volume = {11},
year = {2015}
}
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RIS format (EndNote, RefMan)

TY  - JOUR
AB  - Nonadiabatic dynamics in the vicinity of conical intersections is of essential importance in photochemistry. It is well known that if the branching space is represented in polar coordinates, then for a geometry represented by angle θ, the corresponding adiabatic states are obtained from the diabatic states with the mixing angle θ/2. In an equivalent way, one can study the relation between the real rotation of diabatic states and the resulting nuclear gradient. In this work, we extend the concept to allow a complex rotation of diabatic states to form a nonstationary superposition of electronic states. Our main result is that this leads to an elliptical transformation of the effective potential energy surfaces; i.e., the magnitude of the initial nuclear gradient changes as well as its direction. We fully explore gradient changes that result from varying both θ and  (the complex rotation angle) as a way of electronically controlling nuclear motion, through Ehrenfest dynamics simulations for benzene cation.
AU  - Robb,MA
AU  - Meisner,J
AU  - Vacher,M
AU  - Bearpark,M
DO  - 10.1021/acs.jctc.5b00364
EP  - 3122
PY  - 2015///
SN  - 1549-9618
SP  - 3115
TI  - Geometric rotation of the nuclear gradient at a conical intersection: Extension to complex rotation of diabatic states
T2  - Journal of Chemical Theory and Computation
UR  - http://dx.doi.org/10.1021/acs.jctc.5b00364
UR  - http://hdl.handle.net/10044/1/25985
VL  - 11
ER  -
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