Simulating core electron binding energies of halogenated species adsorbed on ice surfaces and in solution with relativistic quantum embedding calculations

TL;DR

This study combines advanced relativistic quantum embedding calculations with molecular dynamics to accurately simulate core electron binding energies of halogen species on ice and in water, revealing environmental effects on spectra.

Contribution

It introduces a novel computational approach integrating DFT and relativistic coupled cluster methods via FDE for environment-sensitive core binding energy predictions.

Findings

Reproduces experimental trends in core binding energy shifts from water to ice environments.

Water valence band energies are accurately predicted and stable across environments.

Overestimation of halide core binding energies is common, but good agreement is achieved for chloride in water and ice.

Abstract

In this work we investigate the effects of the environment on the X-ray photoelectron spectra of hydrogen chloride and the chloride ions adsorbed on ice surfaces, as well as of chloride ions in water droplets. In our approach, we combine a density functional theory (DFT) description of the ice surface with that of the halogen species with the recently developed relativistic core-valence separation equation of motion coupled cluster (CVS-EOM-IP-CCSD) via the frozen density embedding formalism (FDE), to determine the K and L$_{1,2,3}$ edges of chlorine. Our calculations, which incorporate temperature effects through snapshots from classical molecular dynamics simulations, are shown to reproduce experimental trends in the change of the core binding energies for Cl$^-$ upon moving from a liquid (water droplets) to an interfacial (ice quasi-liquid layer) environment. Our simulations yield water valence band binding energies in good agreement with experiment, and that vary little between the droplets and the ice surface. For the halide core binding energies there is an overall trend of overestimating experimental values, though good agreement between theory and experiment is found for Cl$^-$ in water droplets and on ice. For HCl on the other hand there are significant discrepancies between experimental and calculated core binding energies when we consider structural models which maintain the H-Cl bond more or less intact. An analysis of models that allow for pre-dissociated and dissociated structures suggests that experimentally observed chemical shifts in binding energies between Cl$^-$ snd HCl would reqire that H$^+$ (in the form of H$_3$O$^+$) and Cl$^-$ are separated by roughly 4-6 A.