Molecular orbital tomography beyond the plane wave approximation

Abstract

The use of plane wave approximation in molecular orbital tomography via high-order harmonic generation has been questioned since it was proposed, owing to the fact that it ignores the essential property of the continuum wave function. To address this problem, we develop a theory to retrieve the valence molecular orbital directly utilizing molecular continuum wave function which takes into account the influence of the parent ion field on the continuum electrons. By transforming this wave function into momentum space, we show that the mapping from the relevant molecular orbital to the high-order harmonic spectra is still invertible. As an example, the highest orbital of $\mathrm{N_2}$ is successfully reconstructed and it shows good agreement with the \emph{ab initio} orbital. Our work clarifies the long-standing controversy and strengthens the theoretical basis of molecular orbital tomography.