Geometry-Dependent Nonlocal Valence Screening Following Core Ionization of the Water Dimer

Abstract

Core ionization is spatially localized, but the correlated valence response that screens the resulting hole need not be. Using the water dimer as a minimal hydrogen-bonded system, we ask whether acceptor-site O~1s ionization recruits valence channels on the neighboring donor molecule and how proton displacement redistributes that response. We introduce correlated shifted-start real-time $Λ$-coupled-cluster theory to connect the core-hole spectrum with orbital- and fragment-resolved screening pathways. At equilibrium, the satellite response contains donor-local and intermolecular charge-transfer-like contributions. Their intermolecular origin is supported by the strong suppression of both contributions when the monomers are separated. In a fixed-nuclei geometry scan, elongating the hydrogen-bonded donor O--H bond nearly doubles their combined share of the satellite response, while analysis of the first approximately 10~fs of the fixed-nuclei electronic response reveals stronger modulation involving a donor-localized valence orbital. More broadly, this work shows how localized core ionization can serve as a site-selective probe of electronic communication, with satellite structure revealing how nuclear geometry redirects many-electron screening through molecular environments.