Chemically Assisted Precompression of Hydrogen Molecules in Alkaline-Earth Tetrahydrides.

Abstract

Through a series of high pressure diamond anvil experiments, we report the synthesis of alkaline earth (Ca, Sr, Ba) tetrahydrides, and investigate their properties through Raman spectroscopy, X-ray diffraction, and density functional theory calculations. The tetrahydrides incorporate both atomic and quasi-molecular hydrogen, and we find that the frequency of the intramolecular stretching mode of the units downshifts from Ca to Sr and to Ba upon compression. The experimental results indicate that the larger the host cation, the longer the bond. Analysis of the electron localization function (ELF) demonstrates that the lengthening of the H–H bond is caused by the charge transfer from the metal to and by the steric effect of the metal host on the H–H bond. This effect is most prominent for BaH4, where the precompression of units at 50 GPa results in bond lengths comparable to that of pure H2 above 275 GPa.