Core-ionization spectrum of liquid water

Abstract

We present state-of-the-art calculations of the core-ionization spectrum of water. Despite significant progress in procedures developed to mitigate various experimental complications and uncertainties, the experimental determination of ionization energies of solvated species involves several non-trivial steps such as assessing the effect of the surface potential, electrolytes, and finite escape depths of photoelectrons. This provides a motivation to obtain robust theoretical values of the intrinsic bulk ionization energy and the corresponding solvent-induced shift. Here we develop theoretical protocols based on coupled-cluster theory and electrostatic embedding. Our value of the intrinsic solvent-induced shift of the 1s_O ionization energy of water is −1.79 eV. The computed absolute position and the width of the 1s_O peak in photoelectron spectrum of water are 538.47 eV and 1.44 eV, respectively, agreeing well with the best experimental values.