On the quantum and classical control of laser-driven isomerization in the Wigner representation

Abstract

We investigate the validity of the classical approximation to the numerically exact quantum dynamics for infrared laser-driven control of isomerization processes. To this end, we simulate the fully quantum mechanical dynamics both by wavepacket propagation in position space and by propagating the Wigner function in phase space employing a quantum-mechanical correction term. A systematic comparison is made with purely classical propagation of the Wigner function. On the example of a one-dimensional double well potential, we identify two complementary classes of pulse sequences that invoke either a quantum mechanically or a classically dominated control mechanism. The quantum control relies on a sequence of excitations and de-excitations between the system’s eigenstates on a time scale far exceeding the characteristic vibrational oscillation periods. In contrast, the classical control mechanism is based on a short and strong few-cycle field exerting classical-like forces driving the wavepacket to the target potential well where it is slowed down and finally trapped. While in the first case, only the quantum mechanical propagation correctly describes the field-induced population transfer, the short pulse case is also amenable to a purely classical description. These findings shed light on the applicability of classical approximations to simulate laser-controlled dynamics and may offer a guideline for novel control experiments in more complex systems that can be analyzed and interpreted utilizing efficient state-of-the-art classical trajectory simulations based on ab initio molecular dynamics.

Quantum dynamics with ab initio potentials

“…The work of Petersen et al, applying optical control theory to a tunneling problem, completes this survey of semiclassical phase-space dynamics. 57 Nonadiabatic transitions on multiple coupled PESs add an additional non-classical feature in photochemical dynamics. A rigorous and accurate treatment of quantum dynamics on multi-dimensional nonadiabatically coupled PESs is particularly challenging because of the large excess energy that becomes available in radiationless electronic transitions.…”