Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 11, Issue 7, Pages 3115-3122Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jctc.5b00364
Keywords
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Funding
- UK-EPSRC [EP/I032517/1]
- German Research Foundation (DFG) within the Cluster of Excellence in Simulation Technology [EXC 310/2]
- EPSRC [EP/K039946/1, EP/I032517/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/I032517/1, EP/K039946/1] Funding Source: researchfish
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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 theta, the corresponding adiabatic states are obtained from the diabatic states with the mixing angle theta/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 theta and phi (the complex rotation angle) as a way of electronically controlling nuclear motion, through Ehrenfest dynamics simulations for benzene cation.
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