Calibrating TDDFT Calculations of the X-ray Emission Spectrum of Liquid Water: The Effects of Hartree–Fock Exchange

[Image: see text] The structure and dynamics of liquid water continue to be debated, with insight provided by, among others, X-ray emission spectroscopy (XES), which shows a split in the high-energy 1b(1) feature. This split is yet to be reproduced by theory, and it remains unclear if these difficulties are related to inaccuracies in dynamics simulations, spectrum calculations, or both. We investigate the performance of different methods for calculating XES of liquid water, focusing on the ability of time-dependent density functional theory (TDDFT) to reproduce reference spectra obtained by high-level coupled cluster and algebraic-diagrammatic construction scheme calculations. A metric for evaluating the agreement between theoretical spectra termed the integrated absolute difference (IAD), which considers the integral of shifted difference spectra, is introduced and used to investigate the performance of different exchange-correlation functionals. We find that computed spectra of symmetric and asymmetric model water structures are strongly and differently influenced by the amount of Hartree–Fock exchange, with best agreement to reference spectra for ∼40–50%. Lower percentages tend to yield high density of contributing states, resulting in too broad features. The method introduced here is useful also for other spectrum calculations, in particular where the performance for ensembles of structures are evaluated.