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Geometrical decomposition of nonadiabatic interactions to collective coordinates in many-dimensional and many-state
1Fukui Institute for Fundamental Chemistry, Kyoto University, 606-8103 Kyoto, Japan.
Abstract:
In general, for many-dimensional and many-state nonadiabatic dynamics composed of slow and fast modes, we geometrically decompose the nonadiabatic interactions by means of the method of singular value decomposition. Each pair of the left and right singular vectors connecting the slow (nuclear) and fast (electronic) modes gives rise to a one-dimensional collective coordinate, and the sum of them amounts to the total nonadiabatic interaction. The analysis identifies how efficiently the slow modes, thus decomposed, can induce a transition in their fast counterparts. We discuss the notions of nonadiabatic resonance and nonadiabatic chaos in terms of the decomposition.
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