On Prediction of a Novel Chiral Material Y2H3O(OH): A Hydroxyhydride Holding Hydridic and Protonic Hydrogens

Abstract

Examination of possible pathways of how oxygen atoms can be added to a yttrium oxyhydride system allowed us to predict new derivatives such as hydroxyhydrides possessing the composition M2H3O(OH) (M = Y, Sc, La, and Gd) in which three different anions (H-, O2−, and OH-) share the common chemical space. The crystal data of the solid hydroxyhydrides obtained on the base of DFT modeling correspond to the tetragonal structure that is characterized by the chiral space group P 4 1 . The analysis of bonding situation in M2H3O(OH) showed that the microscopic mechanism governing chemical transformations is caused by the displacements of protons which are induced by interaction with oxygen atoms incorporated into the crystal lattice of the bulk oxyhydride. The oxygen-mediated transformation causes a change in the charge state of some adjacent hydridic sites, thus forming protonic sites associated with hydroxyl groups. The predicted materials demonstrate a specific charge ordering that is associated with the chiral structural organization of the metal cations and the anions because their lattice positions form helical curves spreading along the tetragonal axis. Moreover, the effect of spatial twisting of the H- and H+ sites provides additional linking via strong dihydrogen bonds. The structure–property relationships have been investigated in terms of structural, mechanical, electron, and optical features. It was shown that good polar properties of the materials make them possible prototypes for the design of nonlinear optical systems.

Optical properties of yttrium oxyhydrides: A comparative analysis with experiment

“…As compared with the host metal hydride, the ground state of the oxyhydride system demonstrates better compositional and structural stability; its macroscopic mechanical properties appear to be similar to those of crystalline complex oxides. All together, the anions are committed to successful transformation of the local environment into the complex subsystem of strongly localized charges that may facilitate the dynamically changing interplay of the anions of different structural units [9,11]. This opens a large potential in the development of the functional properties associated with optical and electronic responses.…”