Lattice dynamics of high-pressure hydrides studied by inelastic neutron scattering

Journal of Alloys and Compounds. 2022. Vol. 905. Article 164208.

Antonov Vladimir E., Fedotov V., Ivanov A., Kolesnikov A., Kuzovnikov M., Tkacz M., Yartys V.

Due to the small mass and anomalously large neutron scattering cross-section of proton (about 80 barns compared to a few barns for other nuclei), inelastic neutron scattering is considered as one of the most effective tools in studying optical vibrations of hydrogen atoms in metal hydrides. The current review is focused on the binary hydrides of 3d- and 4d-metals of groups VI–VIII, which were produced at high hydrogen pressures of several gigapascals in relatively large quantities of hundreds of mg, quenched to low temperature and studied by INS ex situ at ambient pressure with high statistical accuracy. One of the unusual effects revealed by INS is a strong increase in the strength of the metal-hydrogen interactions with decreasing atomic number of the d-metal accompanied by an increase in the Me-H distance. Based on the available experimental results, the spectra g(E) of the phonon density of states and temperature dependencies CV(T) of the heat capacity at constant volume at T up to 1000 K have been derived in this paper and presented both in the figures and in digital form. This provides the reference data for the theoretical investigations of the crystal structures and compositions of new practically important hydrides giving the opportunity to validate calculation methods by comparing the calculated g(E) and CV(T) with the accurate experimental dependencies for the binary hydrides. Recent INS studies showed [R.A. Klein et al., J. Alloy. Compd. 894 (2022) 162381] that the fingerprints of anomalously short H-H separations of 1.6 Å violating the “2 Å rule” can be easily and unambiguously identified in the complex INS spectra of quaternary hydrides (La,Ce)NiInH1+x. This makes neutron spectroscopy an attractive means for obtaining valuable data in the search for novel hydrides with a record high hydrogen capacity.

Keywords: фононы, heat capacity, теплоемкость, phonons, High pressure, высокое давление, hydrides, гидриды, Inelastic neutron scattering, неупругое рассеяние нейтронов