Correct Asymptotic Wavefunctions for Calculating Photoelectron Angular Distributions of O2- and NO-

Abstract

The ab initio calculation of photoelectron angular distributions (PADs) for negative ions remains a significant theoretical challenge. In this work, we report a joint experimental and theoretical investigation of PADs for a series of molecular anions with varying polarities, including the nonpolar O2-, the weakly polar NO-, and the strongly polar AsO- and SbO-. To accurately describe the long-range electronic wavefunctions -- where photodetachment contributes most strongly -- we modified the standard Gaussian-type orbitals (GTOs) by augmenting them with a correct exponential Slater-tail basis set (~e^(-ξr)). This simple yet effective approach significantly improves the agreement between the experimental and theoretical PADs for O2- and NO-. However, notable discrepancies persist for NO- for transitions to the v = 0 and v = 1 vibrational levels of neutral NO even after this correction. Given that our methodology successfully reproduced PADs for strongly polar anions (e.g., AsO- and SbO-), these residual discrepancies are unlikely to stem from "exit-channel scattering" induced by long-range dipole fields. Instead, we tentatively attribute the failure for NO- to the breakdown of the Born-Oppenheimer approximation or the frozen orbital approximation, arising from the extremely weak binding of the excess electron.