Ab initio studies of ionization potentials of hydrated hydroxide and hydronium

TL;DR

This study uses ab initio molecular dynamics and many-body electron excitation methods to accurately compute ionization potentials of hydrated hydroxide and hydronium ions, revealing the influence of solvation and proton transfer on their electronic properties.

Contribution

It provides a detailed ab initio analysis of ionization potentials in hydrated ions, linking molecular excitations to experimental features and solvation effects.

Findings

Ionization potential distributions match experimental data.

First solvation shell water molecules mainly perturb ionization potentials.

Proton transfer causes delocalized electron excitation and spectral broadening.

Abstract

The ionization potential distributions of hydrated hydroxide and hydronium are computed with many-body approach for electron excitations with configurations generated by {\it ab initio} molecular dynamics. The experimental features are well reproduced and found to be closely related to the molecular excitations. In the stable configurations, the ionization potential is mainly perturbed by water molecules within the first solvation shell. On the other hand, electron excitation is delocalized on both proton receiving and donating complex during proton transfer, which shifts the excitation energies and broadens the spectra for both hydrated ions.