Geometric rotation of the nuclear gradient at a conical intersection:
Extension to complex rotation of diabatic states
Extension to complex rotation of diabatic states
File(s)acs.jctc.5b00364_1.pdf (3 MB)
Published version
Author(s)
Robb, MA
Meisner, J
Vacher, M
Bearpark, M
Type
Journal Article
Abstract
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 ϕ (the complex rotation angle) as a way of electronically controlling nuclear motion, through Ehrenfest dynamics simulations for benzene cation.
Date Issued
2015-06-11
Date Acceptance
2015-06-11
Citation
Journal of Chemical Theory and Computation, 2015, 11 (7), pp.3115-3122
ISSN
1549-9618
Publisher
American Chemical Society
Start Page
3115
End Page
3122
Journal / Book Title
Journal of Chemical Theory and Computation
Volume
11
Issue
7
Copyright Statement
© 2015 American Chemical Society. This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.
License URL
Source Volume Number
11
Publication Status
Published