Revealing the Bonding Nature and Electronic Structure of Early-Transition-Metal Dihydrides

Metal hydrides are potential candidates for applications in hydrogen-related technologies, such as energy storage, hydrogen compression, and hydrogen sensing, to name just a few. However, understanding the electronic structure and chemical environment of hydrogen within them remains a key challenge. This work presents a new analytical pathway to explore these aspects in technologically relevant systems using hard x-ray photoelectron spectroscopy (HAXPES) on thin films of two prototypical metal dihydrides: YH2−𝛿 and Ti⁢H2−𝛿. By taking advantage of the tunability of synchrotron radiation, a nondestructive depth profile of the chemical states is obtained using core-level spectra. Combining experimental valence-band (VB) spectra collected at varying photon energies with theoretical insights from density functional theory (DFT) calculations, a description of the bonding nature and the role of 𝑑 versus 𝑠⁢𝑝 contributions to states near the Fermi energy are provided. Moreover, a reliable determination of the enthalpy of formation is proposed by using experimental values of the energy position of metal 𝑠-band features close to the Fermi energy in the HAXPES VB spectra.