Many-body effects in the X-ray absorption spectra of liquid water

X-ray absorption spectroscopy (XAS) is a powerful experimental technique to probe the local order in materials with core electron excitations. Experimental interpretation requires supporting theoretical calculations. For water, these calculations are very demanding and, to date, could only be done with major approximations that limited the accuracy of the calculated spectra. This prompted an intense debate on whether a substantial revision of the standard picture of tetrahedrally bonded water was necessary to improve the agreement of theory and experiment. Here, we report a first-principles calculation of the XAS of water that avoids the approximations of prior work, thanks to recent advances in electron excitation theory. The calculated XAS spectra, and their variation with changes of temperature and/or with isotope substitution, are in good quantitative agreement with experiments. The approach requires accurate quasiparticle wave functions beyond density functional theory approximations, accounts for the dynamics of quasiparticles, and includes dynamic screening as well as renormalization effects due to the continuum of valence-level excitations. The three features observed in the experimental spectra are unambiguously attributed to excitonic effects. The pre-edge feature is associated with a bound intramolecular exciton, the main-edge feature is associated with an exciton localized within the coordination shell of the excited molecule, and the post-edge feature is delocalized over more distant neighbors, as expected for a resonant state. The three features probe the local order at short, intermediate, and longer range relative to the excited molecule. The calculated spectra are fully consistent with a standard tetrahedral picture of water.



*This work was primarily supported by the Computational Chemical Center: Chemistry in Solution and at Interfaces funded by the DoE under Award No. DE-SC0019394, and also supported by the Center for Computational Study of Excited-State Phenomena in Energy Materials (C2SEPEM) at the Lawrence Berkeley National Laboratory funded by the DOE under Contract No. DE-AC02-05CH11231.