A Lanthanum-Filled Carbon-Boron Clathrate.

We report a carbon-boron clathrate with composition 2 La@B C (LaB C ). Like recently reported SrB C , single-crystal X-ray diffraction and computational modelling indicate that the isostructural La member crystallizes in the cubic bipartite sodalite structure (Type-VII clathrate) with La atoms encapsulated within truncated octahedral cages composed of alternating carbon and boron atoms. The covalent nature of the B-C bonding results in a hard, incompressible framework, and owing to the balanced electron count, La [B C ] exhibits markedly improved pressure stability and is a semiconductor with an indirect band gap predicted near 1.

Carbon-boron clathrates as a new class of sp-bonded framework materials.

Carbon-based frameworks composed of sp bonding represent a class of extremely lightweight strong materials, but only diamond and a handful of other compounds exist despite numerous predictions. Thus, there remains a large gap between the number of plausible structures predicted and those synthesized. We used a chemical design principle based on boron substitution to predict and synthesize a three-dimensional carbon-boron framework in a host/guest clathrate structure.

Hydrogen-Bonding Modification in Biuret Under Pressure.

Biuret (CHNO) has been studied to 30 GPa by Raman spectroscopy and 50 GPa by X-ray diffraction. Raman peaks exhibit shoulders and splitting that suggests that the molecules undergo reorientation in response to compression. These are observed in three pressure ranges: the first from 3-5 GPa, the second from 8-12 GPa, and finally from 16-20 GPa.

Cyanoacetohydrazide under Pressure: Chemical Changes in a Hydrogen-Bonded Material.

Cyanoacetohydrazide (CAH, C3H5N3O) has been studied under pressure using diamond anvil cell techniques. CAH was characterized using Raman spectroscopy to 30 GPa and synchrotron X-ray diffraction to 45 GPa. The Raman spectra of CAH show reasonable qualitative agreement with first-principle calculations.

Hydrogen bonding induced proton exchange reactions in dense D2-NH3 and D2-CH4 mixtures.

We have investigated high-pressure behaviors of simple binary mixtures of NH3 and D2 to 50 GPa and CH4 and D2 to 30 GPa using confocal micro-Raman spectroscopy. The spectral data indicate strong proton exchange reactions occur in dense D2-NH3 mixture, producing different isotopes of ammonia such as NH3, NH2D, NHD2, and ND3. In contrast, the proton exchange process in dense D2-CH4 mixture is highly limited, and no vibration feature is apparent for deuterated methane.

H2O and D2 mixtures under pressure: spectroscopy and proton exchange kinetics.

We have investigated the pressure-induced spectral changes and the proton exchange reactions of D(2)-H(2)O mixtures to 64 GPa using micro-Raman spectroscopy. The results show the profound difference in the rotational and vibrational Raman spectra of hydrogen isotopes from those of the pure samples, showing the vibrational modes at higher frequencies and continuing to increase with pressure without apparent turnover. This indicates the repulsive nature of D(2)-H(2)O interaction without hydrogen bonds between the two and, thus, interstitial fillings of D(2) molecules into the bcc-like ice lattice.