Electronic-state chaos, intramolecular electronic energy redistribution, and chemical bonding in persisting multidimensional nonadiabatic systems

Abstract

We study the chaotic, huge fluctuation of electronic state, resultant intramolecular energy redistribution, and strong chemical bonding surviving the fluctuation with exceedingly long lifetimes of highly excited boron clusters. Those excited states constitute densely quasi-degenerate state manifolds. The huge fluctuation is induced by persisting multidimensional nonadiabatic transitions among the states in the manifold. We clarify the mechanism of their coexistence and its physical significance. In doing so, we concentrate on two theoretical aspects. One is quantum chaos and energy randomization, which are to be directly extracted from the properties of the total electronic wavefunctions. The present dynamical chaos takes place through frequent transitions from adiabatic states to others, thereby making it very rare for the system to find dissociation channels. This phenomenon leads to the concept of what we call intramolecular nonadiabatic electronic-energy redistribution, which is an electronic-state generaliztion of the notion of intramolecular vibrational energy redistribution. The other aspect is about the peculiar chemical bonding. We investigate it with the energy natural orbitals (ENOs) to see what kind of theoretical structures lie behind the huge fluctuation. The ENO energy levels representing the highly excited states under study appear to have four robust layers. We show that the energy layers responsible for chaotic dynamics and those for chemical bonding are widely separated from each other, and only when an event of what we call “inter-layer crossing” happens to burst can the destruction of these robust energy layers occur, resulting in molecular dissociation. This crossing event happens only rarely because of the large energy gaps between the ENO layers. It is shown that the layers of high energy composed of complex-valued ENOs induce the turbulent flow of electrons and electronic-energy in the cluster. In addition, the random and fast time-oscillations of those high energy ENOs serve as a random force on the nuclear dynamics, which can work to prevent a concentration of high nuclear kinetic energy in the dissociation channels.