Open-Shell Molecules as Sensitive Probes of Spin-Orbit-Controlled Surface Electronic Structure
Abstract
Open-shell molecules are highly sensitive probes of correlated oxide surfaces because their partially occupied frontier orbitals strongly amplify subtle changes in adsorbate-substrate hybridization. Combining infrared reflection-absorption spectroscopy with hybrid density functional theory including non-collinear magnetism and spin-orbit coupling, we show that inclusion of spin-orbit coupling is essential to reproduce the vibrational spectrum of NO adsorbed on UO(111) by suppressing an otherwise artificial overhybridization between the NO frontier orbitals and uranium 5f states. While spin-orbit coupling determines the position of the N-O stretching and, dispersion-driven intermolecular interactions account for its asymmetric broadening at monolayer coverage. These results establish open-shell molecules as sensitive probes of spin-orbit-controlled surface electronic structure and identify NO/UO(111) as a stringent benchmark for electronic-structure methods describing open-shell molecule-surface interactions.
Cite
@article{arxiv.2607.28797,
title = {Open-Shell Molecules as Sensitive Probes of Spin-Orbit-Controlled Surface Electronic Structure},
author = {Solange Mariel Di Napoli and Alexei Nefedov and María Andrea Barral and Gustavo E. Murgida and Ana María Llois and Christof Wöll and M. Verónica Ganduglia-Pirovano and Verónica Laura Vildosola},
journal= {arXiv preprint arXiv:2607.28797},
year = {2026}
}