Photodetachment spectra of lanthanide oxide clusters: prevalence and importance of shake-up transitions.

Abstract

Lanthanides are ubiquitous in technologies used in daily life. The properties of lanthanide-based bulk and nanoscale materials are governed by the unique electronic structures of the lanthanide atoms, which are readily probed via atomic and small-molecule spectroscopy. In this perspective, we introduce an accessible framework for understanding the electronic structures of lanthanide molecules. We then focus on photodetachment spectroscopies, which provide rich molecular and electronic structural information for both anion and neutral charge states. Efforts to map the electronic structures of neutrals using photodetachment of negative ions is further enriched by the effects of strong photoelectron-valence electron interactions, uniquely pronounced in lanthanide-based molecular systems, that drive multi-electron shake-up transitions. We additionally explore some of the computational and theoretical challenges and opportunities arising in this chemical-physical space, including how the kinetic energy of the ejected electron can influence the final shake-up state populations. Results hold the promise to inform development of exciting new applications in a range of technologies.