On Prediction of a Novel Chiral Material Y(2)H(3)O(OH): A Hydroxyhydride Holding Hydridic and Protonic Hydrogens

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 M(2)H(3)O(OH) (M = Y, Sc, La, and Gd) in which three different anions (H(-), O(2)−, 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 [Formula: see text]. The analysis of bonding situation in M(2)H(3)O(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.