Coupled nuclear and electron dynamics in the vicinity of a conical intersection

TL;DR

This paper develops a quantum mechanical approach to simulate coupled nuclear and electron dynamics near conical intersections, demonstrating control of molecular dynamics using tailored laser pulses.

Contribution

It introduces an expanded NEMol ansatz for accurately modeling coupled nuclear-electron dynamics and applies it to control molecular behavior near conical intersections.

Findings

Successful simulation of coupled dynamics in NO2 near a conical intersection

Demonstration of control over molecular passage through the conical intersection using CEP-stabilized pulses

Insights into coherent electron dynamics induced by non-adiabatic coupling

Abstract

Ultrafast optical techniques allow to study ultrafast molecular dynamics involving both nuclear and electronic motion.To support interpretation, theoretical approaches are needed that can describe both the nuclear and electron dynamics.Hence, we revisit and expand our ansatz for the coupled description of the nuclear and electron dynamics in molecular systems (NEMol). In this purely quantum mechanical ansatz the quantum-dynamical description of the nuclear motion is combined with the calculation of the electron dynamics in the eigenfunction basis. The NEMol ansatz is applied to simulate the coupled dynamics of the molecule NO2 in the vicinity of a conical intersection (CoIn) with a special focus on the coherent electron dynamics induced by the non-adiabatic coupling. Furthermore, we aim to control the dynamics of the system when passing the CoIn. The control scheme relies on the carrier envelope phase (CEP) of a few-cycle IR pulse. The laser pulse influences both the movement of the nuclei and the electrons during the population transfer through the CoIn.