Exploring dynamical electron theory beyond the Born–Oppenheimer framework: from chemical reactivity to non-adiabatically coupled electronic and nuclear wavepackets on-the-fly under laser field

摘要: Chemical theory and its application to dynamical electrons in molecules under intense electromagnetic fields is explored, which we take an explicit account of nuclear nonadiabatic (kinematic) interactions along with simultaneous coupling optical interactions. All the electronic wavefunctions studied here are necessarily time-dependent, thereby beyond stationary state quantum chemistry based on Born–Oppenheimer framework. As a general tractable alternative framework track dynamics, propose on-the-fly method calculate electron wavepackets coupled branching non-Born–Oppenheimer paths, through their bifurcations, strong entanglement between motions, coherence decoherence among phases associated them properly represented. Some illustrative numerical examples also reported, aimed at our final goals; real time tracking states, chemical dynamics densely degenerate states motions manipulation and/or creation new terms lasers, so on. Other presented as how wavepacket can be used analyze reactions, shedding light some typical conventional reactions such proton transfer followed by tautomerization.