Molecular wave-packet dynamics on laser-controlled transition states

TL;DR

This study investigates how ultrafast laser pulses can control molecular dissociation dynamics, specifically in H₂⁺, by manipulating vibrational states and transition states, providing insights for quantum control of chemical reactions.

Contribution

It demonstrates control over nuclear motion through transition states using pump-probe laser techniques and semi-classical models, advancing molecular quantum control methods.

Findings

Nuclear motion can be controlled by varying pump-probe delay.

Dynamics are accurately modeled by semi-classical trajectories.

Insights applicable to ultrafast proton-involving reactions.

Abstract

Understanding and controlling the electronic as well as ro-vibrational motion and, thus, the entire chemical dynamics in molecules is the ultimate goal of ultrafast laser and imaging science. In photochemistry, laser-induced dissociation has become a valuable tool for modification and control of reaction pathways and kinetics. Here, we present a pump-probe study of the dissociation dynamics of H$_2^+$ using ultrashort extreme-ultraviolet (XUV) and near-infrared (IR) laser pulses. The reaction kinematics can be controlled by varying the pump-probe delay. We demonstrate that the nuclear motion through the transition state can be reduced to isolated pairs of initial vibrational states. The dynamics is well reproduced by intuitive semi-classical trajectories on a time-dependent potential curve. From this most fundamental scenario we gain insight in the underlying mechanisms which can be applied as design principles for molecular quantum control, particularly for ultrafast reactions involving protons.