Single-electron quantum dynamics in high-harmonic generation spectrum from LiH molecule: Analysis of potential energy surfaces for electrons constructed from a model of localized Gaussian wave packets with valence-bond spin-coupling.

Abstract

A high-harmonic generation (HHG) spectrum from a LiH molecule induced by an intense laser pulse is computed and analyzed with potential energy surfaces for electron motion (ePES) constructed from a model of localized electron wave packets with valence-bond spin-coupling. The molecule has two valence ePES with binding energies of 0.39 hartree and 1.1 hartree. The HHG spectrum from an electron dynamics on the weaker bound valence ePES, virtually assigned to Li 2s, exhibits a dominant peak at the first harmonic without plateau and cutoff. This compares with the free electron spectrum under an oscillating laser field and is comprehensive with the shape and depth of the ePES. The other valence ePES, assigned to H 1s, is deeper bound such that the overall profile of the wave function is well approximated by a Gaussian of the width comparable to the Li-H bond length. However, a small fraction, less than 10-3, of the probability density amplitude tunnels out from the bound potential with high wave number and spreads over tens of nm with parts recombining to the molecule due to the laser field oscillation. This minor portion of the electronic wave function is the major origin of the HHG extending up to 50 harmonic orders. Nonlinear dynamics within the potential well induced by the laser field oscillation also contributes to the HHG up to 30 harmonic orders.