Electronic control of initial nuclear dynamics adjacent to a conical intersection. Article - Mai 2015

Morgane Vacher, Jan Meisner, David Mendive-Tapia, Michael Bearpark, Michael Robb

Morgane Vacher, Jan Meisner, David Mendive-Tapia, Michael Bearpark, Michael Robb, « Electronic control of initial nuclear dynamics adjacent to a conical intersection.  », Journal of Physical Chemistry A, mai 2015, pp. 5165-72. ISSN 1089-5639

Abstract

Photoionization can create a nonstationary electronic state and therefore initiates coupled electron-nuclear dynamics in molecules. Using a CASSCF implementation of the Ehrenfest method, we study the nuclear dynamics following vertical ionization of toluene, starting close to the conical intersection between ground and first excited states of its cation. The results show how the initial nuclear dynamics is controlled by the nonstationary electronic state character. In particular, ionization of this system leading to an equal superposition of the two lowest energy states can initiate nuclear dynamics in an orthogonal direction in the branching space to dynamics on the ground or first excited state potential energy surfaces alone.

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