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Cazorla et al. [preceding comment] criticize our recent results on the high-PT phase diagram of CaF2 (Phys. Rev. B 95, 054118 (2017)). According to our analysis, Cazorla et al. have not converged their calculations with respect to simulation cell size, undermining the comments conclusions about both the high-T behaviour of the P-62m-CaF2 polymorph, and the use of the QHA in our work. As such, we take this opportunity to emphasise the importance of correctly converging molecular dynamics simulations to avoid finite-size errors. We compare our quasiharmonic phase diagram for CaF2 with currently available experimental data, and find it to be entirely consistent and in qualitative agreement with such data. Our prediction of a superionic phase transition in P-62m-CaF2 (made on the basis of the QHA) is shown to be accurate, and we argue that simple descriptors, such as phonon frequencies, can offer valuable insight and predictive power concerning superionic behaviour.
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We investigate the high-pressure behaviour of beryllium, magnesium and calcium difluorides using ab initio random structure searching and density functional theory (DFT) calculations, over the pressure range 0-70 GPa. Beryllium fluoride exhibits extensive polymorphism at low pressures, and we find two new phases for this compound - the silica moganite and CaCl2 structures - which are stable over the wide pressure range 12-57 GPa. For magnesium fluoride, our searching results show that the orthorhombic `O-I TiO2 structure (Pbca, Z=8) is stable for this compound between 40 and 44 GPa. Our searches find no new phases at the static-lattice level for calcium difluoride between 0 and 70 GPa; however, a phase with P62m symmetry is close to stability over this pressure range, and our calculations predict that this phase is stabilised at high temperature. The P62m structure exhibits an unstable phonon mode at large volumes which may signal a transition to a superionic state at high temperatures. The Group-II difluorides are isoelectronic to a number of other AB2-type compounds such as SiO2 and TiO2, and we discuss our results in light of these similarities.
The issues raised in the comment by T.A. Manz are addressed through the presentation of calculated atomic charges for NaF, NaCl, MgO, SrTiO$_3$ and La$_2$Ce$_2$O$_7$, using our previously presented method for calculating Hirshfeld-I charges in Solids [J. Comput. Chem.. doi: 10.1002/jcc.23088]. It is shown that the use of pseudo-valence charges is sufficient to retrieve the full all-electron Hirshfeld-I charges to good accuracy. Furthermore, we present timing results of different systems, containing up to over $200$ atoms, underlining the relatively low cost for large systems. A number of theoretical issues is formulated, pointing out mainly that care must be taken when deriving new atoms in molecules methods based on expectations for atomic charges.
BaFe2Se3 is a potential superconductor material exhibiting transition at 11 K and ambient pressure. Here we extended the structural and performed electrical resistivity measurements on this compound up to 51 GPa and 20 GPa, respectively, in order to distinguish if the superconductivity in this sample is intrinsic to the BaFe2Se3 phase or if it is originating from minor FeSe impurities that show a similar superconductive transition temperature. The electrical resistance measurements as a function of pressure show that at 5 GPa the superconducting transition is observed at around 10 K, similar to the one previously observed for this sample at ambient pressure. This indicates that the superconductivity in this sample is intrinsic to the BaFe2Se3 phase and not to FeSe with Tc > 20 K at these pressures. Further increase in pressure suppressed the superconductive signal and the sample remained in an insulating state up to the maximum achieved pressure of 20 GPa. Single-crystal and powder X-ray diffraction measurements revealed two structural transformations in BaFe2Se3: a second order transition above 3.5 GPa from Pnma (CsAg2I3-type structure) to Cmcm (CsCu2Cl3-type structure) and a first order transformation at 16.6 GPa. Here, {gamma}-BaFe2Se3 transforms into {delta}-BaFe2Se3 (Cmcm, CsCu2Cl3-type average structure) via a first order phase transition mechanism. This transitions is characterized by a significant shortening of the b lattice parameter of {gamma}-BaFe2Se3 (17%) and accompanied by an anisotropic expansion in the orthogonal ac plane at the transition point.
A study of high pressure solid Te was carried out at room temperature using Raman spectroscopy and Density Functional Theory (DFT) calculations. The analysis of the P-dependence of the experi- mental phonon spectrum reveals the occurrence of phase transitions at 4 GPa and 8 GPa confirming the high-pressure scenario recently proposed. The effects of the incommensurate lattice modulation on the vibrational properties of Te is discussed. DFT calculations agree with present and previous experimental data and show the metallization process at 4 GPa being due to the development of charge-bridges between atoms belonging to adjacent chains. A first-principles study of the stability of the 4 GPa phase is reported and discussed also in the light of the insurgence of lattice modulation.
This Comment points out a number of errors in the recent paper by Zarechnaya, Dubrovinskaia, Dubrovinsky, et al. (Phys. Rev. Lett. 102, 185501 (2009)). Results and conclusions presented by Zarechnaya et al. (2009) are either incorrect or have been presented before.
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