Multielectron corrections in molecular high-order harmonic generation for different formulations of the strong-field approximation

TL;DR

This paper evaluates how different formulations of the dipole operator influence multielectron effects in molecular high-order harmonic generation, revealing that certain forms produce physically consistent results while multielectron corrections have limited spectral impact.

Contribution

It provides a detailed comparison of dipole operator forms in the strong-field approximation and assesses their effect on multielectron corrections in HHG spectra for molecules.

Findings

Velocity form incorrectly predicts zero dipole moment in heteronuclear molecules

Length form yields physically consistent non-zero dipole moments

Multielectron corrections have minimal impact on the harmonic spectrum

Abstract

We make a detailed assessment of which form of the dipole operator to use in calculating high order harmonic generation within the framework of the strong field approximation, and look specifically at the role the form plays in the inclusion of multielectron effects perturbatively with regard to the contributions of the highest occupied molecular orbital. We focus on how these corrections affect the high-order harmonic spectra from aligned homonuclear and heteronuclear molecules, exemplified by $\mathrm{N}_2$ and CO, respectively, which are isoelectronic. We find that the velocity form incorrectly finds zero static dipole moment in heteronuclear molecules. In contrast, the length form of the dipole operator leads to the physically expected non-vanishing expectation value for the dipole operator in this case. Furthermore, the so called "overlap" integrals, in which the dipole matrix element is computed using wavefunctions at different centers in the molecule, are prominent in the first-order multielectron corrections for the velocity form, and should not be ignored. Finally, inclusion of the multielectron corrections has very little effect on the spectrum. This suggests that relaxation, excitation and the dynamic motion of the core are important in order to describe multielectron effects in molecular high-order high harmonic generation.