First-principles study of lithium-doped carbon clathrates under pressure

We present a theoretical study on the behavior under pressure of the two hypothetical C$_{46}$ and Li$_8$C$_{46}$ type-I carbon clathrates in order to bring new informations concerning their synthesis. Using \textit{ab initio} calculations, we have explored the energetic and structural properties under pressure of these two carbon based cage-like materials. These low-density meta-stable phases show large negative pressure transitions compared to diamond which represent a serious obstacle for their synthesis. However, we evidence that a minimum energy barrier can be reached close to 40 GPa, suggesting that the synthesis of the Li-clathrate under extreme conditions of pressure and temperature may be possible. Electronic band structure with related density of states behavior under pressure as well as the dependence of the active Raman modes with pressure are also examined

High-pressure Raman study of Fe(IO3)3: Soft-mode behavior driven by coordination changes of iodine atoms

This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpcc.0c06541.[EN] We report high-pressure Raman spectroscopy studies of Fe(IO3)(3) up to nearly 21 GPa that have been interpreted with the help of density functional theory calculations, which include the calculation of phonon dispersion curves and elastic constants at different pressures. Zero-pressure Raman-active mode frequencies and their pressure dependences have been determined. Modes have been assigned and correlated to atomic movements with the help of calculations. Interestingly, in the high-frequency region, there are several modes that soften under compression. These modes have been identified as internal vibrations of the IO3 coordination polyhedron. Their unusual behavior is a consequence of the changes induced by pressure in the coordination sphere of iodine, which gradually change from a threefold coordination to an almost sixfold coordination under compression. The coordination change is favored by the decrease of the stereoactivity of the iodine lone electron pair so that likely a real sixfold coordination is attained after a first-order phase transition previously reported to occur above 21 GPa. The strong nonlinear behavior found in Raman-active modes as well as in theoretically calculated elastic constants has been discovered to be related to the occurrence of two previously unreported isostructural phase transitions at 1.5-2.0 and 5.7-6.0 GPa as shown by dynamic instabilities close to the Brillouin zone center.This work was supported by the Spanish Ministry of Science, Innovation and Universities, the Spanish Research Agency (AEI), the European Fund for Regional Development (ERDF, FEDER) under grants MAT2016-75586-C4-1/2/3-P, PID2019-106383GB-C41/42/43, and RED2018-102612-T (MALTA Consolider-Team Network), and the Generalitat Valenciana under grant Prometeo/2018/123 (EFIMAT). A.L. and D.E. would like to thank the Generalitat Valenciana for the Ph.D. fellowship GRISOLIAP/2019/025).Liang, A.; Rahman, S.; Rodriguez-Hernandez, P.; Muñoz, A.; Manjón, F.; Nenert, G.; Errandonea, D. (2020). High-pressure Raman study of Fe(IO3)3: Soft-mode behavior driven by coordination changes of iodine atoms. The Journal of Physical Chemistry C. 124(39):21329-21337. https://doi.org/10.1021/acs.jpcc.0c06541S21329213371243

Structural and Luminescence Properties of Cu(I)X-Quinoxaline under High Pressure (X = Br, I)

A study of high-pressure single-crystal X-ray diffraction and luminescence experiments together with ab initio simulations based on the density functional theory has been performed for two isomorphous copper(I) halide compounds with the empirical formula [C8H6Cu2X2N2] (X = Br, I) up to 4.62(4) and 7.00(4) GPa for X-ray diffraction and 6.3(4) and 11.6(4) GPa for luminescence, respectively. An exhaustive study of compressibility has been completed by means of determination of the isothermal equations of state and structural changes with pressure at room temperature, giving bulk moduli of K0 = 14.4(5) GPa and K′0 = 7.7(6) for the bromide compound and K0 = 13.0(2) GPa and K′0 = 7.4(2) for the iodide compound. Both cases exhibited a phase transition of second order around 3.3 GPa that was also detected in luminescence experiments under the same high-pressure conditions, wherein redshifts of the emission bands with increasing pressure were observed due to shortening of the Cu–Cu distances. Additionally, ab initio studies were carried out which confirmed the results obtained experimentally, although unfortunately, the phase transition was not predicted

Equation of state and structural characterization of Cu 4 I 4 {PPh 2 (CH 2 CH = CH 2 )} 4 under pressure

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Anomální Ramanovy módy v teluridech

Two anomalous broad bands are usually found in the Raman spectrum of bulk and 2D Te-based chalcogenides, which include binary compounds, like ZnTe, CdTe, HgTe, GaTe, GeTe, SnTe, PbTe, GeTe2, As2Te3, Sb2Te3, Bi2Te3, NiTe2, IrTe2, and TiTe2, as well as ternary compounds, like GaGeTe, SnSb2Te4, SnBi2Te4, and GeSb2Te5. Many different explanations have been proposed in the literature for the origin of the anomalous broad bands in tellurides, usually located between 119 and 145 cm(-1). They have been attributed to the intrinsic Raman modes of the sample, to oxidation of the sample, to the folding of Brillouin-edge modes onto the zone center, to the existence of a double resonance, like that of graphene, or to the formation of Te precipitates. In this paper, we provide arguments to demonstrate that such bands correspond to clusters or precipitates of trigonal Te in the form of nanosize or microsize grains or layers that are segregated either inside or at the surface of the samples. Several mechanisms for Te segregation are discussed and sample heating caused by excessive laser power during Raman scattering measurements is emphasized. Besides, we show that anomalous Raman modes related to Se precipitates also occur in selenides, thus providing a general vision for better characterization of selenides and tellurides by means of Raman scattering measurements and for a better understanding of chalcogenides in general.V Ramanově spektru mnoha chalkogenidů na bázi Te se obvykle nacházejí dva široké pásy. Ty se objevují v binárních sloučeninách jako je ZnTe, CdTe, HgTe, GaTe, GeTe, SnTe, PbTe, GeTe2, As2Te3, Sb2Te3, Bi2Te3, NiTe2, IrTe2, TiTe2, stejně tak jako v ternárních sloučeninách, jako je GaGeTe, SnSb2Te4, SnBi2Te4 a GeSb2Te5. Tyto dva široké anomální pásy se obvykle nalézají mezi 119 a 145 cm-1 . V literatuře nalézáme mnoho různých vysvětlení původu těchto dvou pásů v telluridech. Jsou připisovány vlastnímu vzorku, oxidaci, skládání Brillouin-edge módů do středu zóny, existenci dvojité rezonance, jako je např. u grafenu, nebo tvorbě Te precipitátů. V tomto článku předkládáme argumenty, které ukazují, že takové pásy odpovídají právě shlukům nebo precipitátům trigonálního Te ve formě nano- nebo mikro-zrn nebo vrstev, které jsou segregovány buď uvnitř nebo na povrchu vzorku. Diskutujeme několik mechanismů pro segregaci Te a dále vliv zahřívání vzorku na tuto segregaci v důsledku nadměrného výkonu laseru během měření Ramanova rozptylu. Dále ukazujeme, že anomální Ramanovy módy související s precipitáty Se se obecně vyskytují také v selenidech. Tyto závěry poskytují obecný pohled na charakterizaci selenidů a teluridů pomocí Ramanova rozptylu usnadňují pochopení chalkogenidů obecně