The importance for the global carbon cycle, the P–T phase diagram of CaCO3 has been under extensive investigation since the invention of the high-pressure techniques. However, this study is far from being completed. In the present work, we show the existence of two new high-pressure polymorphs of CaCO3. The crystal structure prediction performed here reveals a new polymorph corresponding to distorted aragonite structure and named aragonite-II. In situ diamond anvil cell experiments confirm the presence of aragonite-II at 35 GPa and allow identification of another high-pressure polymorph at 50 GPa, named CaCO3-VII. CaCO3-VII is a structural analogue of CaCO3-P21/c-l, predicted theoretically earlier. The P–T phase diagram obtained based on a quasi-harmonic approximation shows the stability field of CaCO3-VII and aragonite-II at 30–50 GPa and 0–1200 K. Synthesized earlier in experiments on cold compression of calcite, CaCO3-VI was found to be metastable in the whole pressure–temperature range.

A comprehensive P-V-T dataset for bcc-Mo was obtained at pressures up to 31 GPa and temperatures from 300 to 1673 K using MgO and Au pressure calibrants. The thermodynamic analysis of these data was performed using high-temperature Birch-Murnaghan (HTBM) equations of state (EOS), Mie-Grüneisen-Debye (MGD) relation combined with the room-temperature Vinet EOS, and newly proposed Kunc-Einstein (KE) approach. The analysis of room-temperature compression data with the Vinet EOS yields V0 = 31.14 ± 0.02 Å3, KT = 260 ± 1 GPa, and KT′ = 4.21 ± 0.05. The derived thermoelastic parameters for the HTBM include (∂KT/∂T)P = −0.019 ± 0.001 GPa/K and thermal expansion α = a0 + a1T with a0 = 1.55 ( ± 0.05) × 10−5 K−1 and a1 = 0.68 ( ± 0.07) × 10−8 K−2. Fitting to the MGD relation yields γ0 = 2.03 ± 0.02 and q = 0.24 ± 0.02 with the Debye temperature (θ0) fixed at 455-470 K. Two models are proposed for the KE EOS. The model 1 (Mo-1) is the best fit to our P-V-T data, whereas the second model (Mo-2) is derived by including the shock compression and other experimental measurements. Nevertheless, both models provide similar thermoelastic parameters. Parameters used on Mo-1 include two Einstein temperatures ΘE10 = 366 K and ΘE20 = 208 K; Grüneisen parameter at ambient condition γ0 = 1.64 and infinite compression γ∞ = 0.358 with β  = 0.323; and additional fitting parameters m = 0.195, e0 = 0.9 × 10−6 K−1, and g = 5.6. Fixed parameters include k = 2 in Kunc EOS, mE1 = mE2 = 1.5 in expression for Einstein temperature, and a0 = 0 (an intrinsic anharmonicity parameter). These parameters are the best representation of the experimental data for Mo and can be used for variety of thermodynamic calculations for Mo and Mo-containing systems including phase diagrams, chemical reactions, and electronic structure.

In a wide range of P-T conditions, such fundamental characteristics as compressibility and thermoelastic properties remain unknown for most classes of organic compounds. Here we attempt to clarify this issue by the example of naphthalene as a model representative of polycyclic aromatic hydrocarbons (PAHs). The elastic behavior of solid naphthalene was studied by in situ synchrotron powder X-ray diffraction up to 13 GPa and 773 K and first principles computations to 20 GPa and 773 K. Fitting of the P-V experimental data to Vinet equation of state yielded T 0 = 8.4(3) GPa and T' = 7.2 (3) at V0 = 361 Å(3), whereas the thermal expansion coefficient was found to be extremely low at P > 3 GPa (about 10(-5) K(-1)), in agreement with theoretical estimation. Such a diminishing of thermal effects with the pressure increase clearly demonstrates a specific feature of the high-pressure behavior of molecular crystals like PAHs, associated with a low energy of intermolecular interactions.

Crystals of the Mn Ba(BO)F phase were grown from a high-temperature solution. This new fluoride borate is built of positively charged [Ba(BO)] blocks, the so-called "anti-zeolite" pattern. Using X-ray single-crystal diffraction, the bulk atomic arrangement in the centrosymmetric tetragonal unit cell in I4/ mcm could be elucidated. Crystals of the (MnF) group-containing solid solution Mn Ba(BO)F are dark brown in color in contrast to the differently colored crystals of (LiF) group-containing "anti-zeolite" LiBa(BO)F ( P4 bc). According to the electron spin resonance and optical spectroscopic investigation, the absorption spectrum of LiBa(BO)F crystals results from the absorption of light by both exciton and free charge carriers and can be tuned by varying the initial composition of the high-temperature solution.

The pressure-induced shift of Sm:SrB4O7 fluorescence was calibrated in a quasi-hydrostatic helium medium up to 60 GPa using the recent Sm-doped yttrium-aluminum garnet primary pressure scale as a reference. The resulting calibration can be written as P = −2836/14.3 [(1 + Δλ/685.51)−14.3 − 1]. Previous calibrations based on the internally inconsistent primary scales are revised, and, after appropriate correction, found to agree with the proposed one. The calibration extended to 120 GPa was also performed using corrected previous data and can be written as P = 4.20 Δλ (1 + 0.020 Δλ)/(1 + 0.036 Δλ).

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