New determination of structure parameters in strong field tunneling ionization theory of molecules

TL;DR

This paper improves the accuracy of molecular orbital wavefunctions in strong field tunneling ionization theory by constructing a DFT-based model potential and iteratively refining asymptotic wavefunctions, leading to better ionization probability predictions.

Contribution

The authors develop a method to accurately determine asymptotic wavefunctions and structure parameters for molecules, enhancing tunneling ionization models.

Findings

Improved asymptotic wavefunctions using an iterative DFT-based approach.

Enhanced agreement with experimental ionization measurements.

Better prediction of alignment-dependent ionization probabilities.

Abstract

In the strong field molecular tunneling ionization theory of Tong et al. [Phys. Rev. A 66, 033402 (2002)], the ionization rate depends on the asymptotic wavefunction of the molecular orbital from which the electron is removed. The orbital wavefunctions obtained from standard quantum chemistry packages in general are not good enough in the asymptotic region. Here we construct a one-electron model potential for several linear molecules using density functional theory (DFT). We show that the asymptotic wavefunction can be improved with an iteration method and after one iteration accurate asymptotic wavefunctions and structure parameters are determined. With the new parameters we examine the alignment-dependent tunneling ionization probabilities for several molecules and compare with other calculations and with recent measurements, including ionization from inner molecular orbitals.