2021/11/27 by Richard Asamoah Opoku, Opoku, Richard Asamoah, Céline Toubin +3
Earth and Planetary Sciences · Physics and Astronomy · #Advanced Chemical Physics Studies #Atmospheric Ozone and Climate #Atmospheric chemistry and aerosols #Chemical Physics (physics.chem-ph) #FOS: Physical sciences
paper · pdf · doi:10.48550/arxiv.2111.13909
openalex publication_date 2021/11/27 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
We report an investigation of the suitability of quantum embedding for\nmodeling the effects of the environment on the X-ray photoelectron spectra of\nhydrogen chloride and the chloride ions adsorbed on ice surfaces, as well as of\nchloride ions in water droplets. In our approach, we combine a density\nfunctional theory (DFT) description of the ice surface with that of the halogen\nspecies with the recently developed relativistic core-valence separation\nequation of motion coupled cluster (CVS-EOM-IP-CCSD) via the frozen density\nembedding formalism (FDE), to determine the K and L1,2,3 edges of\nchlorine. Our calculations, which incorporate temperature effects through\nsnapshots from classical molecular dynamics simulations, are shown to reproduce\nthe experimental trends for L edges of the species on ice surfaces, with\nrespect to changes in temperature as well as the decrease in core binding\nenergies in Cl- with respect to HCl. Finally, we find that in contrast to\nthe L edges, we strongly underestimate the environmental effects on the K\nedges. We trace this behavior to the inability of the embedding potential\nobtained with the FDE approach to faithfully reproduce the Kohn-Sham potential\nof the analogous DFT calculation on the whole (supermolecular) system, and\nprovide an ad hoc correction to the CVS-EOM-IP-CCSD energies, based on\nground-state DFT calculations, that yields binding energies with similar\naccuracy to that observed for the L edges.\n