Abstract
The study of coupled electron-nuclear dynamics driven by coherent superpositions of electronic states is now possible in attosecond science experiments. The objective is to understand the electronic control of chemical reactivity. In this work we report coherent 8-state non-adiabatic electron-nuclear dynamics simulations of the benzene radical cation. The computations were inspired by the extreme ultraviolet (XUV) experimental results in which all 8 electronic states were prepared with significant population. Our objective was to study the nuclear dynamics using various bespoke coherent electronic state superpositions as initial conditions in the Quantum-Ehrenfest method. The original XUV measurements were supported by Multi-configuration time-dependent Hartree (MCTDH) simulations, which suggested a model of successive passage through conical intersections. The present computations support a complementary model where non-adiabatic events are seen far from a conical intersection and are controlled by electron dynamics involving non-adjacent adiabatic states. It proves to be possible to identify two superpositions that can be linked with two possible fragmentation paths.
Highlights
The study of coupled electron-nuclear dynamics driven by coherent superpositions of electronic states is possible in attosecond science experiments
We illustrate this idea with the eight lowest energy states of the benzene cation, which has been the subject of recent experimental work[12] using extremely short extreme ultraviolet (XUV) pulses obtained by means of highorder harmonic generation (HHG)
We have shown that the non-adiabatic effects associated with coherent superpositions can be seen far from the conical intersection and may be partly responsible for fragmentation
Summary
The study of coupled electron-nuclear dynamics driven by coherent superpositions of electronic states is possible in attosecond science experiments. Our strategy in this paper involves the study of non-adiabatic dynamics of a coherent superposition of the electronic states of benzene.
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