Potential energy surfaces for electron dynamics modeled by floating and breathing Gaussian wave packets with valence-bond spin-coupling: An analysis of high-harmonic generation spectrum

TL;DR

This paper models high-harmonic generation in LiH using localized electron wave packets with valence-bond spin-coupling, successfully reproducing spectral features and revealing electron contributions.

Contribution

It introduces a localized EWP model with valence-bond spin-coupling to analyze HHG spectra, providing insights beyond conventional molecular orbital approaches.

Findings

Reproduces HHG spectrum features consistent with previous methods

Identifies dominant contributions from H 1s and Li 2s electrons

Shows incoherent sum of single-electron responses suffices for spectrum

Abstract

A model of localized electron wave packets (EWPs), floating and breathing Gaussians with non-orthogonal valence-bond spin-coupling, is applied to compute the high-harmonic generation (HHG) spectrum from a LiH molecule induced by an intense laser pulse. The characteristic features of the spectrum, a plateau up to 50 harmonic-order and a cut-off, agreed well with those from the previous time-dependent complete active-space self-consistent-field calculation [T. Sato and K. L. Ishikawa, Phys. Rev. A \textbf{91}, 023417 (2015)]. In contrast with the conventional molecular orbital picture in which the Li 2s and H 1s atomic orbitals are strongly mixed, the present calculation indicates that an incoherent sum of responses of single electrons reproduces the HHG spectrum, in which the contribution from H 1s electron dominates the plateau and cut-off, whereas the Li 2s electron contributes to the lower frequency response. The results are comprehensive in terms of the shapes of single-electron potential energy curves constructed from the localized EWP model.