Towards attochemistry: Control of nuclear motion through conical intersections and electronic coherences

TL;DR

This paper explores how conical intersections and electronic coherences influence nuclear motion, demonstrating that phase imprinting can steer nuclear wavepackets, paving the way for attochemistry control.

Contribution

It introduces a model showing how conical intersections enable control of nuclear dynamics via electronic coherence and phase imprinting.

Findings

Non-adiabatic coupling near Franck-Condon point preserves electronic coherence.

Phase imprinting can steer nuclear wavepackets through conical intersections.

Conical intersections are essential for attochemistry control.

Abstract

The effect of nuclear dynamics and conical intersections on electronic coherences is investigated employing a two-state, two-mode linear vibronic coupling model. Exact quantum dynamical calculations are performed using the multi-configuration time-dependent Hartree method (MCTDH). It is found that the presence of a non-adiabatic coupling close to the Franck-Condon point can preserve electronic coherence to some extent. Additionally, the possibility of steering the nuclear wavepackets by imprinting a relative phase between the electronic states during the photoionization process is discussed. It is found that the steering of nuclear wavepackets is possible given that a coherent electronic wavepacket embodying the phase difference passes through a conical intersection. A conical intersection close to the Franck-Condon point is thus a necessary prerequisite for control, providing a clear path towards attochemistry.