Disponibilidad léxica sobre palabras específicas en estudiantes de Educación Secundaria de Almería

Resumen basado en el de la publicaciónTítulo, resumen y palabras clave también en inglésSiguiendo la tradición previa de investigación sobre didáctica de la lengua y disponibilidad léxica, se presentan los resultados de la aplicación de una prueba asociativa a una muestra de cuatrocientos estudiantes de Educación Secundaria, durante el curso académico 1998-1999, en la ciudad de Almería (España). El objetivo del trabajo consistió en determinar los usos específicos de palabras basadas en dieciocho centros de interés. Es decir, se examinaron palabras de registro coloquial, extranjerismos, formas dialecto-patrimoniales, marcas, siglas y abreviaturas. Finalmente, se proporciona un análisis de estos grupos léxico-semánticos, desde una perspectiva descriptiva, que permite conocer mejor el vocabulario específico con el que cuentan los discentes en este nivel de enseñanza.ES

Vibrational properties of CdGa2S4 at high pressure

[EN] Raman scattering measurements have been performed in cadmium digallium sulphide (CdGa2S4) with defect chalcopyrite structure up to 25 GPa in order to study its pressure-induced phase transitions. These measurements have been complemented and compared with latticedynamics ab initio calculations including the TO-LO splitting at high pressures in order to provide a better assignment of experimental Raman modes. In addition, experimental and theoretical Gruneisen parameters have been reported in order to calculate the molar heat capacity and thermal expansion coefficient of CdGa2S4. Our measurements provide evidence that CdGa2S4 undergoes an irreversible phase transition above 15 GPa to a Raman-inactive phase, likely with a disordered rock salt structure. Moreover, the Raman spectrum observed on downstroke from 25 GPa to 2 GPa has been attributed to a new phase, tentatively identified as a disordered zinc blende structure, that undergoes a reversible phase transition to the Raman-inactive phase above 10 GPa. Published under license by AIP Publishing.The authors thank the financial support of the Spanish Ministerio de Economia y Competitividad (MINECO) under Grant Nos. MAT2016-75586-C4-2/3-P and MAT2015-71070-REDC (MALTA Consolider) and the Generalitat Valenciana under Project No. PROMETEO/2018/123-EFIMAT. E. P.-G., A. M., and P. R.-H. acknowledge computing time provided by Red Espanola de Supercomputacion (RES) and MALTA-Cluster.Gallego-Parra, S.; Gomis, O.; Vilaplana Cerda, RI.; Ortiz, H.; Perez-Gonzalez, E.; Luna Molina, R.; Rodríguez-Hernández, P.... (2019). Vibrational properties of CdGa2S4 at high pressure. Journal of Applied Physics. 125(11):1-12. https://doi.org/10.1063/1.5080503S11212511Gomis, O., Santamaría-Pérez, D., Vilaplana, R., Luna, R., Sans, J. A., Manjón, F. J., … Ursaki, V. V. (2014). Structural and elastic properties of defect chalcopyrite HgGa2S4 under high pressure. Journal of Alloys and Compounds, 583, 70-78. doi:10.1016/j.jallcom.2013.08.123Cohen, M. L. (1985). Calculation of bulk moduli of diamond and zinc-blende solids. Physical Review B, 32(12), 7988-7991. doi:10.1103/physrevb.32.7988Kim, J. W., & Kim, Y. J. (2007). Optical Properties of Eu Doped M-Ga2S4 (M:Zn, Ca, Sr) Phosphors for White Light Emitting Diodes. Journal of Nanoscience and Nanotechnology, 7(11), 4065-4068. doi:10.1166/jnn.2007.066Yu, R., Noh, H. M., Moon, B. K., Choi, B. C., Jeong, J. H., Jang, K., … Jang, J. K. (2013). Photoluminescence properties of a new red-emitting Mn-activated ZnGa2S4 phosphor. Materials Research Bulletin, 48(6), 2154-2158. doi:10.1016/j.materresbull.2013.02.017Liang, F., Kang, L., Lin, Z., Wu, Y., & Chen, C. (2017). Analysis and prediction of mid-IR nonlinear optical metal sulfides with diamond-like structures. Coordination Chemistry Reviews, 333, 57-70. doi:10.1016/j.ccr.2016.11.012Sahariya, J., Kumar, P., & Soni, A. (2017). Structural and optical investigations of ZnGa2X4 (X = S, Se) compounds for solar photovoltaic applications. Materials Chemistry and Physics, 199, 257-264. doi:10.1016/j.matchemphys.2017.07.003Syrbu, N. N., Tiron, A. V., Parvan, V. I., Zalamai, V. V., & Tiginyanu, I. M. (2015). Interference of birefractive waves in CdGa2S4 crystals. Physica B: Condensed Matter, 463, 88-92. doi:10.1016/j.physb.2015.02.007Vilaplana, R., Gomis, O., Manjón, F. J., Ortiz, H. M., Pérez-González, E., López-Solano, J., … Tiginyanu, I. M. (2013). Lattice Dynamics Study of HgGa2Se4at High Pressures. The Journal of Physical Chemistry C, 117(30), 15773-15781. doi:10.1021/jp402493rGrzechnik, A., Ursaki, V. V., Syassen, K., Loa, I., Tiginyanu, I. M., & Hanfland, M. (2001). Pressure-Induced Phase Transitions in Cadmium Thiogallate CdGa2Se4. Journal of Solid State Chemistry, 160(1), 205-211. doi:10.1006/jssc.2001.9224Gomis, O., Vilaplana, R., Manjón, F. J., Ruiz-Fuertes, J., Pérez-González, E., López-Solano, J., … Tiginyanu, I. M. (2015). HgGa2 Se4 under high pressure: An optical absorption study. physica status solidi (b), 252(9), 2043-2051. doi:10.1002/pssb.201451714Rahnamaye Aliabad, H. A., Basirat, S., & Ahmad, I. (2017). Structural, electronical and thermoelectric properties of CdGa2S4 compound under high pressures by mBJ approach. Journal of Materials Science: Materials in Electronics, 28(21), 16476-16483. doi:10.1007/s10854-017-7559-1Ursaki, V. V., Burlakov, I. I., Tiginyanu, I. M., Raptis, Y. S., Anastassakis, E., & Anedda, A. (1999). Phase transitions in defect chalcopyrite compounds under hydrostatic pressure. Physical Review B, 59(1), 257-268. doi:10.1103/physrevb.59.257Klotz, S., Chervin, J.-C., Munsch, P., & Le Marchand, G. (2009). Hydrostatic limits of 11 pressure transmitting media. Journal of Physics D: Applied Physics, 42(7), 075413. doi:10.1088/0022-3727/42/7/075413Blöchl, P. E. (1994). Projector augmented-wave method. Physical Review B, 50(24), 17953-17979. doi:10.1103/physrevb.50.17953Kresse, G., & Furthmüller, J. (1996). Efficient iterative schemes forab initiototal-energy calculations using a plane-wave basis set. Physical Review B, 54(16), 11169-11186. doi:10.1103/physrevb.54.11169Baroni, S., de Gironcoli, S., Dal Corso, A., & Giannozzi, P. (2001). Phonons and related crystal properties from density-functional perturbation theory. Reviews of Modern Physics, 73(2), 515-562. doi:10.1103/revmodphys.73.515Perdew, J. P., Ruzsinszky, A., Csonka, G. I., Vydrov, O. A., Scuseria, G. E., Constantin, L. A., … Burke, K. (2008). Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces. Physical Review Letters, 100(13). doi:10.1103/physrevlett.100.136406Sans, J. Á., Santamaría-Pérez, D., Popescu, C., Gomis, O., Manjón, F. J., Vilaplana, R., … Tiginyanu, I. M. (2014). Structural and Vibrational Properties of CdAl2S4under High Pressure: Experimental and Theoretical Approach. The Journal of Physical Chemistry C, 118(28), 15363-15374. doi:10.1021/jp5037926Lottici, P. P., & Razzetti, C. (1984). Raman scattering in mixed defect chalcopyrite crystals. Journal of Molecular Structure, 115, 133-136. doi:10.1016/0022-2860(84)80032-0Kerimova, T. G., Abdullaev, N. A., Mamedova, I. A., Badalova, Z. I., Guliev, R. A., Paucar, R., … Mamedov, N. T. (2013). Optical phonons in CdGa2S4x Se4(1 − x) alloys. Semiconductors, 47(6), 761-766. doi:10.1134/s1063782613060110Tiginyanu, I. M., Lottici, P. P., Razzetti, C., & Gennari, S. (1993). Effects of the Cations on the Raman Spectra of Sulphur Defect Chalcopyrites. Japanese Journal of Applied Physics, 32(S3), 561. doi:10.7567/jjaps.32s3.561Kerimova, T. G., Mamedova, I. A., Abdullayev, N. A., Asadullayeva, S. Q., & Badalova, Z. I. (2014). Raman scattering in ZnGa2Se4 single crystals. Semiconductors, 48(7), 868-871. doi:10.1134/s1063782614070112Razzetti, C., & Lottici, P. P. (1993). Raman Scattering in Defective AIIB2IIIX4VICompounds and Alloys. Japanese Journal of Applied Physics, 32(S3), 431. doi:10.7567/jjaps.32s3.431Syrbu, N. N., Nemerenco, L. L., & Cojocaru, O. (2002). Vibrational and Polariton Spectra of CdGa2S4 and CdAl2S4 Crystals. Crystal Research and Technology, 37(1), 101-110. doi:10.1002/1521-4079(200202)37:13.0.co;2-dGomis, O., Vilaplana, R., Manjón, F. J., Santamaría-Pérez, D., Errandonea, D., Pérez-González, E., … Ursaki, V. V. (2013). High-pressure study of the structural and elastic properties of defect-chalcopyrite HgGa2Se4. Journal of Applied Physics, 113(7), 073510. doi:10.1063/1.4792495Gomis, O., Ortiz, H. M., Sans, J. A., Manjón, F. J., Santamaría-Pérez, D., Rodríguez-Hernández, P., & Muñoz, A. (2016). InBO3 and ScBO3 at high pressures: An ab initio study of elastic and thermodynamic properties. Journal of Physics and Chemistry of Solids, 98, 198-208. doi:10.1016/j.jpcs.2016.07.002K. R. Allakhverdiev, Frontiers of High Pressure Research II: Application of High Pressure to Low-Dimensional Novel Electronic Materials (Springer, 2001), p. 99.Lottici, P. P., & Razzetti, C. (1983). A comparison of the raman spectra of ZnGa2Se4 and other gallium defect chalcopyrites. Solid State Communications, 46(9), 681-684. doi:10.1016/0038-1098(83)90506-9Sanjuán, M. L., & Morón, M. C. (2002). Raman study of Zn1−xMnxGa2Se4 diluted magnetic semiconductors: disorder and resonance effects. Physica B: Condensed Matter, 316-317, 565-567. doi:10.1016/s0921-4526(02)00574-4Radautsan, S. I., Tiginyanu, I. M., Ursakii, V. V., Fomin, V. M., & Pokatilov, E. P. (1990). The Peculiarities of the Temperature Broadening of Raman Light Scattering Lines in Zn(Cd)Ga2Se4 Single Crystals. physica status solidi (b), 162(1), K63-K66. doi:10.1002/pssb.2221620143Bernard, J. E., & Zunger, A. (1988). Ordered-vacancy-compound semiconductors: PseudocubicCdIn2Se4. Physical Review B, 37(12), 6835-6856. doi:10.1103/physrevb.37.6835Manjón, F. J., Gomis, O., Vilaplana, R., Sans, J. A., & Ortiz, H. M. (2013). Order-disorder processes in adamantine ternary ordered-vacancy compounds. physica status solidi (b), 250(8), 1496-1504. doi:10.1002/pssb.201248596Mitani, T., Naitou, T., Matsuishi, K., Onari, S., Allakhverdiev, K., Gashimzade, F., & Kerimova, T. (2003). Raman scattering in CdGa2Se4 under pressure. physica status solidi (b), 235(2), 321-325. doi:10.1002/pssb.200301579Meenakshi, S., Vijyakumar, V., Godwal, B. K., Eifler, A., Orgzall, I., Tkachev, S., & Hochheimer, H. D. (2006). High pressure X-ray diffraction study of CdAl2Se4 and Raman study of AAl2Se4 (A=Hg, Zn) and CdAl2X4 (X=Se, S). Journal of Physics and Chemistry of Solids, 67(8), 1660-1667. doi:10.1016/j.jpcs.2006.02.015Manjón, F. J., Marí, B., Serrano, J., & Romero, A. H. (2005). Silent Raman modes in zinc oxide and related nitrides. Journal of Applied Physics, 97(5), 053516. doi:10.1063/1.1856222H. Bilz and W. Kress, Phonon Dispersion Relations in Insulators (Springer, 1979), p. 110.Cheng, Y. C., Jin, C. Q., Gao, F., Wu, X. L., Zhong, W., Li, S. H., & Chu, P. K. (2009). Raman scattering study of zinc blende and wurtzite ZnS. Journal of Applied Physics, 106(12), 123505. doi:10.1063/1.3270401(2017). Theoretical Analysis of Elastic, Mechanical and Phonon Properties of Wurtzite Zinc Sulfide under Pressure. Crystals, 7(6), 161. doi:10.3390/cryst7060161González, J., Fernández, B. J., Besson, J. M., Gauthier, M., & Polian, A. (1992). High-pressure behavior of Raman modes inCuGaS2. Physical Review B, 46(23), 15092-15101. doi:10.1103/physrevb.46.15092Talwar, D. N., Vandevyver, M., Kunc, K., & Zigone, M. (1981). Lattice dynamics of zinc chalcogenides under compression: Phonon dispersion, mode Grüneisen, and thermal expansion. Physical Review B, 24(2), 741-753. doi:10.1103/physrevb.24.741Griesinger, A., Spindler, K., & Hahne, E. (1999). Measurements and theoretical modelling of the effective thermal conductivity of zeolites. International Journal of Heat and Mass Transfer, 42(23), 4363-4374. doi:10.1016/s0017-9310(99)00096-4Hofmeister, A. M., & Mao, H. -k. (2002). Redefinition of the mode Gruneisen parameter for polyatomic substances and thermodynamic implications. Proceedings of the National Academy of Sciences, 99(2), 559-564. doi:10.1073/pnas.241631698Miller, S. A., Gorai, P., Ortiz, B. R., Goyal, A., Gao, D., Barnett, S. A., … Toberer, E. S. (2017). Capturing Anharmonicity in a Lattice Thermal Conductivity Model for High-Throughput Predictions. Chemistry of Materials, 29(6), 2494-2501. doi:10.1021/acs.chemmater.6b04179Zeier, W. G., Zevalkink, A., Gibbs, Z. M., Hautier, G., Kanatzidis, M. G., & Snyder, G. J. (2016). Thinking Like a Chemist: Intuition in Thermoelectric Materials. Angewandte Chemie International Edition, 55(24), 6826-6841. doi:10.1002/anie.201508381Barron, T. H. . (1957). Grüneisen parameters for the equation of state of solids. Annals of Physics, 1(1), 77-90. doi:10.1016/0003-4916(57)90006-4Arora, A. K. (1990). Grüneisen parameter of soft phonons and high pressure phase transitions in semiconductors. Journal of Physics and Chemistry of Solids, 51(4), 373-375. doi:10.1016/0022-3697(90)90122-vGrüneisen, E. (1912). Theorie des festen Zustandes einatomiger Elemente. Annalen der Physik, 344(12), 257-306. doi:10.1002/andp.19123441202Mishra, K. K., Bevara, S., Ravindran, T. R., Patwe, S. J., Gupta, M. K., Mittal, R., … Tyagi, A. K. (2018). High pressure behavior of complex phosphate K2Ce[PO4]2: Grüneisen parameter and anharmonicity properties. Journal of Solid State Chemistry, 258, 845-853. doi:10.1016/j.jssc.2017.12.022Manjon, F. J., Tiginyanu, I., & Ursaki, V. (Eds.). (2014). Pressure-Induced Phase Transitions in AB2X4 Chalcogenide Compounds. Springer Series in Materials Science. doi:10.1007/978-3-642-40367-5Allakhverdiev, K., Gashimzade, F., Kerimova, T., Mitani, T., Naitou, T., Matsuishi, K., & Onari, S. (2003). Raman scattering under pressure in ZnGa2Se4. Journal of Physics and Chemistry of Solids, 64(9-10), 1597-1601. doi:10.1016/s0022-3697(03)00077-5Parlak, C., & Eryiğit, R. (2006). Ab initiovolume-dependent elastic and lattice dynamical properties of chalcopyriteCuGaSe2. Physical Review B, 73(24). doi:10.1103/physrevb.73.245217Kern, G., Kresse, G., & Hafner, J. (1999). Ab initiocalculation of the lattice dynamics and phase diagram of boron nitride. Physical Review B, 59(13), 8551-8559. doi:10.1103/physrevb.59.8551B. A. Weinstein and R. Zallen, Light Scattering in Solids IV (Springer, 1984), p. 463.Schwer, H., & Krämer, V. (1990). The crystal structures of CdAl2S4, HgAl2S4, and HgGa2S4. Zeitschrift für Kristallographie, 190(1-2), 103-110. doi:10.1524/zkri.1990.190.1-2.103Mamedov, K. K., Aliev, M. M., Kerimov, I. G., & Kh. Nani, R. (1972). Heat capacity of AIIB2IIIC4VI-type ternary semiconducting compounds at low temperatures. Physica Status Solidi (a), 9(2), K149-K152. doi:10.1002/pssa.2210090255Quintero, M., Morocoima, M., Guerrero, E., & Ruiz, J. (1994). Temperature variation of lattice parameters and thermal expansion coefficients of the compound MnGa2Se4. Physica Status Solidi (a), 146(2), 587-593. doi:10.1002/pssa.2211460203Ravindran, T. R., Arora, A. K., & Mary, T. A. (2000). High Pressure Behavior ofZrW2O8: Grüneisen Parameter and Thermal Properties. Physical Review Letters, 84(17), 3879-3882. doi:10.1103/physrevlett.84.3879Morocoima, M., Quintero, M., Guerrero, E., Tovar, R., & Conflant, P. (1997). Temperature variation of lattice parameters and thermal expansion coefficients of the compound ZnGa2Se4. Journal of Physics and Chemistry of Solids, 58(3), 503-507. doi:10.1016/s0022-3697(96)00048-

Pressure-induced order-disorder transitions in beta-In2S3: an experimental and theoretical study of structural and vibrational properties.

[EN] This joint experimental and theoretical study of the structural and vibrational properties of beta-In2S3 upon compression shows that this tetragonal defect spinel undergoes two reversible pressure-induced order¿disorder transitions up to 20 GPa. We propose that the first high-pressure phase above 5.0 GPa has the cubic defect spinel structure of alpha-In2S3 and the second high-pressure phase (phi-In2S3) above 10.5 GPa has a defect alpha-NaFeO2-type (R-3m) structure. This phase, related to the NaCl structure, has not been previously observed in spinels under compression and is related to both the tetradymite structure of topological insulators and to the defect LiTiO2 phase observed at high pressure in other thiospinels. Structural characterization of the three phases shows that alpha-In2S3 is softer than beta-In2S3 while phi-In2S3 is harder than beta-In2S3. Vibrational characterization of the three phases is also provided, and their Raman active modes are tentatively assigned. Our work shows that the metastable a phase of In2S3 can be accessed not only by high temperature or varying composition, but also by high pressure. On top of that, the pressure-induced beta¿alpha¿phi sequence of phase transitions evidences that beta-In2S3, a BIII2XV3 compound with an intriguing structure typical of AIIBIII2XVI4 compounds (intermediate between thiospinels and ordered-vacancy compounds) undergoes: (i) a first phase transition at ambient pressure to a disordered spinel-type structure (alpha-In2S3), isostructural with those found at high pressure and high temperature in other BIII2XV3 compounds; and (ii) a second phase transition to the defect alpha-NaFeO2-type structure (phi-In2S3), a distorted NaCl-type structure that is related to the defect NaCl phase found at high pressure in AIIBIII2XVI4 ordered-vacancy compounds and to the defect LiTiO2-type phase found at high pressure in AIIBIII2XVI4 thiospinels. This result shows that In2S3 (with its intrinsic vacancies) has a similar pressure behaviour to thiospinels and ordered-vacancy compounds of the AIIBIII2XVI4 family, making beta-In2S3 the union link between such families of compounds and showing that group-13 thiospinels have more in common with ordered-vacancy compounds than with oxospinels and thiospinels with transition metals.This publication is part of the project MALTA Consolider Team network (RED2018-102612-T), financed by MINECO/AEI/10.13039/501100003329; by I+D+i projects PID2019-106383GB41/42/43, financed by MCIN/AEI/10.13039/501100011033; by project PROMETEO/2018/123 (EFIMAT), financed by Generalitat Valenciana; and by projects DMREF-NSF 1434897 and DOE DE-SC0016176, financed from US agencies. A. M., and P. R.-H. acknowledge computing time provided by Red Espanola de Supercomputacion (RES) and MALTA-Cluster, and we also thank ALBA synchrotron light source for funded experiment 2017022088 at the MSPD-BL04 beamline. A. H. R. acknowledges the computational resources awarded by XSEDE, a project supported by National Science Foundation grant number ACI-1053575, as well as the time from the Super Computing System (Thorny Flat) at WVU, which is funded in part by the National Science Foundation (NSF) Major Research Instrumentation Program (MRI) Award #1726534, and West Virginia University. The authors also acknowledge the support from the Texas Advances Computer Center (with the Stampede2 and Bridges supercomputers). A. M. and R. A. acknowledge the support from Olle Engkvists stiftelse, Sweden, Carl Tryggers Stiftelse for Vetenskaplig Forskning (CTS) and the Swedish Research Council (Grant no. VR-2016-06014 and VR-2020-04410). SNIC and HPC2N are also acknowledged for providing computing resources.Gallego-Parra, S.; Gomis, O.; Vilaplana Cerda, RI.; Cuenca-Gotor, VP.; Martínez-García, D.; Rodríguez-Hernández, P.; Muñoz, A.... (2021). Pressure-induced order-disorder transitions in beta-In2S3: an experimental and theoretical study of structural and vibrational properties. Physical Chemistry Chemical Physics. 23(41):23625-23642. https://doi.org/10.1039/d1cp02969j2362523642234

Orpiment under compression: metavalent bonding at high pressure

[EN] We report a joint experimental and theoretical study of the structural, vibrational, and electronic properties of layered monoclinic arsenic sulfide crystals (a-As2S3), aka mineral orpiment, under compression. X-ray diffraction and Raman scattering measurements performed on orpiment samples at high pressure and combined with ab initio calculations have allowed us to determine the equation of state and the tentative assignment of the symmetry of many Raman-active modes of orpiment. From our results, we conclude that no first-order phase transition occurs up to 25 GPa at room temperature; however, compression leads to an isostructural phase transition above 20 GPa. In fact, the As coordination increases from threefold at room pressure to more than fivefold above 20 GPa. This increase in coordination can be understood as the transformation from a solid with covalent bonding to a solid with metavalent bonding at high pressure, which results in a progressive decrease of the electronic and optical bandgap, an increase of the dielectric tensor components and Born effective charges, and a considerable softening of many high-frequency optical modes with increasing pressure. Moreover, we propose that the formation of metavalent bonding at high pressures may also explain the behavior of other group-15 sesquichalcogenides under compression. In fact, our results suggest that group-15 sesquichalcogenides either show metavalent bonding at room pressure or undergo a transition from p-type covalent bonding at room pressure towards metavalent bonding at high pressure, as a precursor towards metallic bonding at very high pressure.The authors are thankful for the financial support from Spanish Ministerio de Economia y Competitividad (MINECO) through MAT2016-75586-C4-2/3-P, FIS2017-83295-P and MALTA Consolider Team project (RED2018-102612-T). Also from Generalitat Valenciana under project PROMETEO/2018/123-EFIMAT. ELDS acknowledges the European Union FP7 People: Marie-Curie Actions programme for grant agreement No. 785789-COMEX. JAS also acknowledges the Ramon y Cajal program for funding support through RYC-2015-17482. AM, SR and ELDS are thankful for interesting discussions with J. Contreras-Garcia who taught them how to analyze the ELF. Finally, the authors thank the ALBA Light Source for beam allocation at beamline MSPD (Experiment No. 2013110699) and acknowledge computing time provided by MALTACluster and Red Espan~ola de Supercomputacion (RES) through computer resources at MareNostrum with technical support provided by the Barcelona Supercomputing Center (QCM-2018-3-0032).Cuenca-Gotor, VP.; Sans-Tresserras, JÁ.; Gomis, O.; Mujica, A.; Radescu, S.; Muñoz, A.; Rodríguez-Hernández, P.... (2020). Orpiment under compression: metavalent bonding at high pressure. Physical Chemistry Chemical Physics. 22(6):3352-3369. https://doi.org/10.1039/c9cp06298jS33523369226J. D. Smith , J. C.Bailar , H. J.Emeléus and R.Nyholm , The Chemistry of Arsenic, Antimony and Bismuth , Pergamon Texts in Inorganic Chemistry , 1973 , vol. 2Pliny the Elder, Naturalis Historia , ed. J. Bostock and H. T. Riley , Taylor and Francis , London , 1855 , ch. 22E. W. Fitzhugh , Orpiment and Realgar, in Artists’ Pigments , A Handbook of Their History and Characteristics , Oxford University Press , 1997 , vol. 3, pp. 47–80Spurrell, F. C. J. (1895). Notes on Egyptian Colours. Archaeological Journal, 52(1), 222-239. doi:10.1080/00665983.1895.10852669Burgio, L., & Clark, R. J. H. (2000). Comparative pigment analysis of six modern Egyptian papyri and an authentic one of the 13th centuryBC by Raman microscopy and other techniques. Journal of Raman Spectroscopy, 31(5), 395-401. doi:10.1002/1097-4555(200005)31:53.0.co;2-eWaxman, S., & Anderson, K. C. (2001). History of the Development of Arsenic Derivatives in Cancer Therapy. The Oncologist, 6(S2), 3-10. doi:10.1634/theoncologist.6-suppl_2-3Ding, W., Tong, Y., Zhang, X., Pan, M., & Chen, S. (2016). Study of Arsenic Sulfide in Solid Tumor Cells Reveals Regulation of Nuclear Factors of Activated T-cells by PML and p53. Scientific Reports, 6(1). doi:10.1038/srep19793J. Heo and W. J.Chung , Rare-earth-doped chalcogenide glass for lasers and amplifiers , Chalcogenide Glasses: Preparation, Properties and Applications , Woodhead Publishing , 2014 , pp. 347–380D. W. Hewak , N. I.Zheludev and K. F.MacDonald , Controlling light on the nanoscale with chalcogenide thin films , Chalcogenide Glasses: Preparation, Properties and Applications , Woodhead Publishing , 2014 , pp. 471–508MORIMOTO, N. (1954). THE CRYSTAL STRUCTURE OF ORPIMENT (As2S3) REFINED. Mineralogical Journal, 1(3), 160-169. doi:10.2465/minerj1953.1.160Mullen, D. J. E., & Nowacki, W. (1972). Refinement of the crystal structures of realgar, AsS and orpiment, As2S3*. Zeitschrift für Kristallographie, 136(1-2), 48-65. doi:10.1524/zkri.1972.136.1-2.48Kampf, A. R., Downs, R. T., Housley, R. M., Jenkins, R. A., & Hyršl, J. (2011). Anorpiment, As2S3, the triclinic dimorph of orpiment. Mineralogical Magazine, 75(6), 2857-2867. doi:10.1180/minmag.2011.075.6.2857Gibbs, G. V., Wallace, A. F., Zallen, R., Downs, R. T., Ross, N. L., Cox, D. F., & Rosso, K. M. (2010). Bond Paths and van der Waals Interactions in Orpiment, As2S3. The Journal of Physical Chemistry A, 114(23), 6550-6557. doi:10.1021/jp102391aCheng, H., Zhou, Y., & Frost, R. L. (2017). Structure comparison of Orpiment and Realgar by Raman spectroscopy. Spectroscopy Letters, 50(1), 23-29. doi:10.1080/00387010.2016.1277359Porto, S. P. S., & Wood, D. L. (1962). Ruby Optical Maser as a Raman Source. Journal of the Optical Society of America, 52(3), 251. doi:10.1364/josa.52.000251Weber, A., & Porto, S. P. S. (1965). He–Ne Laser as a Light Source for High-Resolution Raman Spectroscopy. Journal of the Optical Society of America, 55(8), 1033. doi:10.1364/josa.55.001033Ward, A. T. (1968). Raman spectroscopy of sulfur, sulfur-selenium, and sulfur-arsenic mixtures. The Journal of Physical Chemistry, 72(12), 4133-4139. doi:10.1021/j100858a031Scheuermann, W., & Ritter, G. J. (1969). Raman Spectra of Cinnabar (HgS), Realgar (As4S4) and Orpiment (As2S3). Zeitschrift für Naturforschung A, 24(3), 408-411. doi:10.1515/zna-1969-0317Zallen, R., Slade, M. L., & Ward, A. T. (1971). Lattice Vibrations and Interlayer Interactions in CrystallineAs2S3andAs2Se3. Physical Review B, 3(12), 4257-4273. doi:10.1103/physrevb.3.4257Zallen, R., & Slade, M. (1974). Rigid-layer modes in chalcogenide crystals. Physical Review B, 9(4), 1627-1637. doi:10.1103/physrevb.9.1627Zallen, R. (1974). Pressure-Raman effects and vibrational scaling laws in molecular crystals:S8andAs2S3. Physical Review B, 9(10), 4485-4496. doi:10.1103/physrevb.9.4485DeFonzo, A. P., & Tauc, J. (1978). Network dynamics of 3:2 coordinated compounds. Physical Review B, 18(12), 6957-6972. doi:10.1103/physrevb.18.6957Razzetti, C., & Lottici, P. P. (1979). Polarization analysis of the Raman spectrum of As2S3 crystals. Solid State Communications, 29(4), 361-364. doi:10.1016/0038-1098(79)90572-6Besson, J. M., Cernogora, J., & Zallen, R. (1980). Effect of pressure on optical properties of crystallineAs2S3. Physical Review B, 22(8), 3866-3876. doi:10.1103/physrevb.22.3866Besson, J. M., Cernogora, J., Slade, M. L., Weinstein, B. A., & Zallen, R. (1981). Pressure effects on the absorption edge, refractive index, and Raman spectra of crystalline and amorphous As2S3. Physica B+C, 105(1-3), 319-323. doi:10.1016/0378-4363(81)90267-9Frost, R. L., Martens, W. N., & Kloprogge, J. T. (2002). Raman spectroscopic study of cinnabar (HgS), realgar (As4S4), and orpiment (As2S3) at 298 and 77K. Neues Jahrbuch für Mineralogie - Monatshefte, 2002(10), 469-480. doi:10.1127/0028-3649/2002/2002-0469Mamedov, S., & Drichko, N. (2018). Characterization of 2D As2S3 crystal by Raman spectroscopy. MRS Advances, 3(6-7), 385-390. doi:10.1557/adv.2018.201Itie, J. P., Polian, A., Grimsditch, M., & Susman, S. (1993). X-Ray Absorption Spectroscopy Investigation of Amorphous and Crystalline As2S3up to 30 GPa. Japanese Journal of Applied Physics, 32(S2), 719. doi:10.7567/jjaps.32s2.719Zallen, R. (2004). Effect of pressure on optical properties of crystalline As2S3. High Pressure Research, 24(1), 117-118. doi:10.1080/08957950410001661945Bolotina, N. B., Brazhkin, V. V., Dyuzheva, T. I., Katayama, Y., Kulikova, L. F., Lityagina, L. V., & Nikolaev, N. A. (2014). High-pressure polymorphism of As2S3 and new AsS2 modification with layered structure. JETP Letters, 98(9), 539-543. doi:10.1134/s0021364013220025Liu, K., Dai, L., Li, H., Hu, H., Yang, L., Pu, C., … Liu, P. (2019). Phase Transition and Metallization of Orpiment by Raman Spectroscopy, Electrical Conductivity and Theoretical Calculation under High Pressure. Materials, 12(5), 784. doi:10.3390/ma12050784Kravchenko, E. A., Timofeeva, N. V., & Vinogradova, G. Z. (1980). Crystal modifications of arsenic and antimony sulphides appearing at high pressure and temperature. Journal of Molecular Structure, 58, 253-262. doi:10.1016/0022-2860(80)85027-7Šiškins, M., Lee, M., Alijani, F., van Blankenstein, M. R., Davidovikj, D., van der Zant, H. S. J., & Steeneken, P. G. (2019). Highly Anisotropic Mechanical and Optical Properties of 2D Layered As2S3 Membranes. ACS Nano, 13(9), 10845-10851. doi:10.1021/acsnano.9b06161Bao, Z., & Chen, X. (2016). Flexible and Stretchable Devices. Advanced Materials, 28(22), 4177-4179. doi:10.1002/adma.201601422Koo, J. H., Kim, D. C., Shim, H. J., Kim, T.-H., & Kim, D.-H. (2018). Flexible and Stretchable Smart Display: Materials, Fabrication, Device Design, and System Integration. Advanced Functional Materials, 28(35), 1801834. doi:10.1002/adfm.201801834Garcia‐Bucio, M. A., Maynez‐Rojas, M. Á., Casanova‐González, E., Cárcamo‐Vega, J. J., Ruvalcaba‐Sil, J. L., & Mitrani, A. (2019). Raman and surface‐enhanced Raman spectroscopy for the analysis of Mexican yellow dyestuff. Journal of Raman Spectroscopy, 50(10), 1546-1554. doi:10.1002/jrs.5729Shportko, K., Kremers, S., Woda, M., Lencer, D., Robertson, J., & Wuttig, M. (2008). Resonant bonding in crystalline phase-change materials. Nature Materials, 7(8), 653-658. doi:10.1038/nmat2226Lee, S., Esfarjani, K., Luo, T., Zhou, J., Tian, Z., & Chen, G. (2014). Resonant bonding leads to low lattice thermal conductivity. Nature Communications, 5(1). doi:10.1038/ncomms4525Li, C. W., Hong, J., May, A. F., Bansal, D., Chi, S., Hong, T., … Delaire, O. (2015). Orbitally driven giant phonon anharmonicity in SnSe. Nature Physics, 11(12), 1063-1069. doi:10.1038/nphys3492Xu, M., Jakobs, S., Mazzarello, R., Cho, J.-Y., Yang, Z., Hollermann, H., … Wuttig, M. (2017). Impact of Pressure on the Resonant Bonding in Chalcogenides. The Journal of Physical Chemistry C, 121(45), 25447-25454. doi:10.1021/acs.jpcc.7b07546Wuttig, M., Deringer, V. L., Gonze, X., Bichara, C., & Raty, J.-Y. (2018). Incipient Metals: Functional Materials with a Unique Bonding Mechanism. Advanced Materials, 30(51), 1803777. doi:10.1002/adma.201803777Raty, J., Schumacher, M., Golub, P., Deringer, V. L., Gatti, C., & Wuttig, M. (2018). A Quantum‐Mechanical Map for Bonding and Properties in Solids. Advanced Materials, 31(3), 1806280. doi:10.1002/adma.201806280Svensson, C. (1974). The crystal structure of orthorhombic antimony trioxide, Sb2O3. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, 30(2), 458-461. doi:10.1107/s0567740874002986Stergiou, A. C., & Rentzeperis, P. J. (1985). The crystal structure of arsenic selenide, As2Se3. Zeitschrift für Kristallographie, 173(3-4), 185-191. doi:10.1524/zkri.1985.173.3-4.185Pertlik, F. (1978). Verfeinerung der Kristallstruktur des Minerals Claudetit, As2O3 (?Claudetit I?). Monatshefte f�r Chemie, 109(2), 277-282. doi:10.1007/bf00906344Brown, A., & Rundqvist, S. (1965). Refinement of the crystal structure of black phosphorus. Acta Crystallographica, 19(4), 684-685. doi:10.1107/s0365110x65004140Efthimiopoulos, I., Zhang, J., Kucway, M., Park, C., Ewing, R. C., & Wang, Y. (2013). Sb2Se3 under pressure. Scientific Reports, 3(1). doi:10.1038/srep02665Efthimiopoulos, I., Kemichick, J., Zhou, X., Khare, S. V., Ikuta, D., & Wang, Y. (2014). High-Pressure Studies of Bi2S3. The Journal of Physical Chemistry A, 118(9), 1713-1720. doi:10.1021/jp4124666Ibáñez, J., Sans, J. A., Popescu, C., López-Vidrier, J., Elvira-Betanzos, J. J., Cuenca-Gotor, V. P., … Muñoz, A. (2016). Structural, Vibrational, and Electronic Study of Sb2S3 at High Pressure. The Journal of Physical Chemistry C, 120(19), 10547-10558. doi:10.1021/acs.jpcc.6b01276Cuenca-Gotor, V. P., Sans, J. A., Ibáñez, J., Popescu, C., Gomis, O., Vilaplana, R., … Bergara, A. (2016). Structural, Vibrational, and Electronic Study of α-As2Te3 under Compression. The Journal of Physical Chemistry C, 120(34), 19340-19352. doi:10.1021/acs.jpcc.6b06049Walsh, A., Payne, D. J., Egdell, R. G., & Watson, G. W. (2011). Stereochemistry of post-transition metal oxides: revision of the classical lone pair model. Chemical Society Reviews, 40(9), 4455. doi:10.1039/c1cs15098gSrivastava, P., Singh Mund, H., & Sharma, Y. (2011). Investigation of electronic properties of crystalline arsenic chalcogenides: Theory and experiment. Physica B: Condensed Matter, 406(15-16), 3083-3088. doi:10.1016/j.physb.2011.05.012Kroumova, E., Aroyo, M. I., Perez-Mato, J. M., Kirov, A., Capillas, C., Ivantchev, S., & Wondratschek, H. (2003). Bilbao Crystallographic Server : Useful Databases and Tools for Phase-Transition Studies. Phase Transitions, 76(1-2), 155-170. doi:10.1080/0141159031000076110Canepa, P., Hanson, R. M., Ugliengo, P., & Alfredsson, M. (2010). J-ICE: a newJmolinterface for handling and visualizing crystallographic and electronic properties. Journal of Applied Crystallography, 44(1), 225-229. doi:10.1107/s0021889810049411Siebert, H. (1954). Kraftkonstante und Strukturchemie. V. Struktur der Sauerstoffs�uren. Zeitschrift f�r anorganische und allgemeine Chemie, 275(4-5), 225-240. doi:10.1002/zaac.19542750407Birch, F. (1938). The Effect of Pressure Upon the Elastic Parameters of Isotropic Solids, According to Murnaghan’s Theory of Finite Strain. Journal of Applied Physics, 9(4), 279-288. doi:10.1063/1.1710417Guńka, P. A., Dranka, M., Hanfland, M., Dziubek, K. F., Katrusiak, A., & Zachara, J. (2015). Cascade of High-Pressure Transitions of Claudetite II and the First Polar Phase of Arsenic(III) Oxide. Crystal Growth & Design, 15(8), 3950-3954. doi:10.1021/acs.cgd.5b00567S. Haussühl , Physical Properties of Crystals. An Introduction , Wiley-VCH , 2007R. J. Angel , 2019 , http://www.rossangel.com/text_strain.htmS. Minomura , K.Aoki , N.Koshizuka and T.Tsushima , High-Pressure Science and Technology , Springer , 1979 , p. 435Bandyopadhyay, A. K., & Singh, D. B. (1999). Pressure induced phase transformations and band structure of different high pressure phases in tellurium. Pramana, 52(3), 303-319. doi:10.1007/bf02828893Efthimiopoulos, I., Buchan, C., & Wang, Y. (2016). Structural properties of Sb2S3 under pressure: evidence of an electronic topological transition. Scientific Reports, 6(1). doi:10.1038/srep24246Manjón, F. J., Vilaplana, R., Gomis, O., Pérez-González, E., Santamaría-Pérez, D., Marín-Borrás, V., … Muñoz-Sanjosé, V. (2013). High-pressure studies of topological insulators Bi2Se3, Bi2Te3, and Sb2Te3. physica status solidi (b), 250(4), 669-676. doi:10.1002/pssb.201200672Sans, J. A., Manjón, F. J., Pereira, A. L. J., Vilaplana, R., Gomis, O., Segura, A., … Ruleova, P. (2016). Structural, vibrational, and electrical study of compressed BiTeBr. Physical Review B, 93(2). doi:10.1103/physrevb.93.024110Pereira, A. L. J., Santamaría-Pérez, D., Ruiz-Fuertes, J., Manjón, F. J., Cuenca-Gotor, V. P., Vilaplana, R., … Sans, J. A. (2018). Experimental and Theoretical Study of Bi2O2Se Under Compression. The Journal of Physical Chemistry C, 122(16), 8853-8867. doi:10.1021/acs.jpcc.8b02194Degtyareva, O., Hernández, E. R., Serrano, J., Somayazulu, M., Mao, H., Gregoryanz, E., & Hemley, R. J. (2007). Vibrational dynamics and stability of the high-pressure chain and ring phases in S and Se. The Journal of Chemical Physics, 126(8), 084503. doi:10.1063/1.2433944Richter, W., Renucci, J. B., & Cardona, M. (1973). Hydrostatic Pressure Dependence of First-Order Raman Frequencies in Se and Te. Physica Status Solidi (b), 56(1), 223-229. doi:10.1002/pssb.2220560120Aoki, K., Shimomura, O., Minomura, S., Koshizuka, N., & Tsushima, T. (1980). Raman Scattering of Trigonal Se and Te at Very High Pressure. Journal of the Physical Society of Japan, 48(3), 906-911. doi:10.1143/jpsj.48.906Lucovsky, G. (1972). A comparison of the long wave optical phonons in trigonal Se and trigonal Te. Physica Status Solidi (b), 49(2), 633-641. doi:10.1002/pssb.2220490226Brown, I. D. (1988). What factors determine cation coordination numbers? Acta Crystallographica Section B Structural Science, 44(6), 545-553. doi:10.1107/s0108768188007712Dudev, M., Wang, J., Dudev, T., & Lim, C. (2006). Factors Governing the Metal Coordination Number in Metal Complexes from Cambridge Structural Database Analyses. The Journal of Physical Chemistry B, 110(4), 1889-1895. doi:10.1021/jp054975nBrown, I. D. (2016). Are covalent bonds really directed? American Mineralogist, 101(3), 531-539. doi:10.2138/am-2016-5299Properzi, L., Polian, A., Munsch, P., & Di Cicco, A. (2013). Investigation of the phase diagram of selenium by means of Raman spectroscopy. High Pressure Research, 33(1), 35-39. doi:10.1080/08957959.2013.769048Marini, C., Chermisi, D., Lavagnini, M., Di Castro, D., Petrillo, C., Degiorgi, L., … Postorino, P. (2012). High-pressure phases of crystalline tellurium: A combined Raman andab initiostudy. Physical Review B, 86(6). doi:10.1103/physrevb.86.064103Cheng, Y., Cojocaru‐Mirédin, O., Keutgen, J., Yu, Y., Küpers, M., Schumacher, M., … Wuttig, M. (2019). Understanding the Structure and Properties of Sesqui‐Chalcogenides (i.e., V 2 VI 3 or Pn 2 Ch 3 (Pn = Pnictogen, Ch = Chalcogen) Compounds) from a Bonding Perspective. Advanced Materials, 31(43), 1904316. doi:10.1002/adma.201904316Vilaplana, R., Gomis, O., Manjón, F. J., Segura, A., Pérez-González, E., Rodríguez-Hernández, P., … Kucek, V. (2011). High-pressure vibrational and optical study of Bi2Te3. Physical Review B, 84(10). doi:10.1103/physrevb.84.104112Fauth, F., Peral, I., Popescu, C., & Knapp, M. (2013). The new Material Science Powder Diffraction beamline at ALBA Synchrotron. Powder Diffraction, 28(S2), S360-S370. doi:10.1017/s0885715613000900Hammersley, A. P., Svensson, S. O., Hanfland, M., Fitch, A. N., & Hausermann, D. (1996). Two-dimensional detector software: From real detector to idealised image or two-theta scan. High Pressure Research, 14(4-6), 235-248. doi:10.1080/08957959608201408Toby, B. H. (2001). EXPGUI, a graphical user interface forGSAS. Journal of Applied Crystallography, 34(2), 210-213. doi:10.1107/s0021889801002242Momma, K., & Izumi, F. (2011). VESTA 3for three-dimensional visualization of crystal, volumetric and morphology data. Journal of Applied Crystallography, 44(6), 1272-1276. doi:10.1107/s0021889811038970Dewaele, A., Loubeyre, P., & Mezouar, M. (2004). Equations of state of six metals above94GPa. Physical Review B, 70(9). doi:10.1103/physrevb.70.094112Mao, H. K., Xu, J., & Bell, P. M. (1986). Calibration of the ruby pressure gauge to 800 kbar under quasi-hydrostatic conditions. Journal of Geophysical Research, 91(B5), 4673. doi:10.1029/jb091ib05p04673Piermarini, G. J., Block, S., & Barnett, J. D. (1973). Hydrostatic limits in liquids and solids to 100 kbar. Journal of Applied Physics, 44(12), 5377-5382. doi:10.1063/1.1662159Klotz, S., Chervin, J.-C., Munsch, P., & Le Marchand, G. (2009). Hydrostatic limits of 11 pressure transmitting media. Journal of Physics D: Applied Physics, 42(7), 075413. doi:10.1088/0022-3727/42/7/075413Hohenberg, P., & Kohn, W. (1964). Inhomogeneous Electron Gas. Physical Review, 136(3B), B864-B871. doi:10.1103/physrev.136.b864Kresse, G., & Hafner, J. (1993). Ab initiomolecular dynamics for liquid metals. Physical Review B, 47(1), 558-561. doi:10.1103/physrevb.47.558Kresse, G., & Furthmüller, J. (1996). Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Computational Materials Science, 6(1), 15-50. doi:10.1016/0927-0256(96)00008-0Blöchl, P. E. (1994). Projector augmented-wave method. Physical Review B, 50(24), 17953-17979. doi:10.1103/physrevb.50.17953Perdew, J. P., Burke, K., & Ernzerhof, M. (1996). Generalized Gradient Approximation Made Simple. Physical Review Letters, 77(18), 3865-3868. doi:10.1103/physrevlett.77.3865Perdew, J. P., Ruzsinszky, A., Csonka, G. I., Vydrov, O. A., Scuseria, G. E., Constantin, L. A., … Burke, K. (2008). Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces. Physical Review Letters, 100(13). doi:10.1103/physrevlett.100.136406Monkhorst, H. J., & Pack, J. D. (1976). Special points for Brillouin-zone integrations. Physical Review B, 13(12), 5188-5192. doi:10.1103/physrevb.13.5188Grimme, S. (2006). Semiempirical GGA-type density functional constructed with a long-range dispersion correction. Journal of Computational Chemistry, 27(15), 1787-1799. doi:10.1002/jcc.20495Contreras-García, J., Pendás, Á. M., Silvi, B., & Manuel Recio, J. (2008). Useful applications of the electron localization function in high-pressure crystal chemistry. Journal of Physics and Chemistry of Solids, 69(9), 2204-2207. doi:10.1016/j.jpcs.2008.03.028Contreras-García, J., Pendás, A. M., Recio, J. M., & Silvi, B. (2008). Computation of Local and Global Properties of the Electron Localization Function Topology in Crystals. Journal of Chemical Theory and Computation

Structural, vibrational and electronic properties of alpha'-Ga2S3 under compression

[EN] We report a joint experimental and theoretical study of the low-pressure phase of ¿¿-Ga2S3 under compression. Theoretical ab initio calculations have been compared to X-ray diffraction and Raman scattering measurements under high pressure carried out up to 17.5 and 16.1 GPa, respectively. In addition, we report Raman scattering measurements of ¿¿-Ga2S3 at high temperature that have allowed us to study its anharmonic properties. To understand better the compression of this compound, we have evaluated the topological properties of the electron density, the electron localization function, and the electronic properties as a function of pressure. As a result, we shed light on the role of the Ga¿S bonds, the van der Waals interactions inside the channels of the crystalline structure, and the single and double lone electron pairs of the sulphur atoms in the anisotropic compression of ¿¿-Ga2S3. We found that the structural channels are responsible for the anisotropic properties of ¿¿-Ga2S3 and the A¿(6) phonon, known as the breathing mode and associated with these channels, exhibits the highest anharmonic behaviour. Finally, we report calculations of the electronic band structure of ¿¿-Ga2S3 at different pressures and find a nonlinear pressure behaviour of the direct band gap and a pressure-induced direct-to-indirect band gap crossover that is similar to the behaviour previously reported in other ordered-vacancy compounds, including ß-Ga2Se3. The importance of the single and, more specially, the double lone electron pairs of sulphur in the pressure dependence of the topmost valence band of ¿¿-Ga2S3 is stressed.The authors thank the financial support from the Spanish Research Agency (AEI) under projects MALTA Consolider Team network (RED2018-102612-T) and projects MAT2016-75586-C4-2/3-P, FIS2017-83295-P, PID2019-106383GB-42/43, and PGC2018-097520-A-100, as well as from Generalitat Valenciana under Project PROMETEO/2018/123 (EFIMAT). A. M. and P. R.-H. acknowledge computing time provided by Red Espanola de Supercomputacion (RES) and MALTA-Cluster and E. L. D. S. acknowledges Marie Sklodowska-Curie Grant No. 785789-COMEX from the European Union's Horizon 2020 research and innovation program. J. A. S. also wants to thank the Ramon y Cajal fellowship (RYC-2015-17482) for financial support. We also thank the ALBA synchrotron light source for funded experiment 2017022088 at the MSPD-BL04 beamline.Gallego-Parra, S.; Vilaplana Cerda, RI.; Gomis, O.; Lora Da Silva, E.; Otero-De-La-Roza, A.; Rodríguez-Hernández, P.; Muñoz, A.... (2021). Structural, vibrational and electronic properties of alpha'-Ga2S3 under compression. Physical Chemistry Chemical Physics. 23(11):6841-6862. https://doi.org/10.1039/d0cp06417cS68416862231

Experimental and Theoretical Study of Bi2O2Se Under Compression

[EN] We report a joint experimental and theoretical study of the structural, vibrational, elastic, optical, and electronic properties of the layered high-mobility semiconductor Bi2O2Se at high pressure. A good agreement between experiments and ab initio calculations is observed for the equation of state, the pressure coefficients of the Raman-active modes and the bandgap of the material. In particular, a detailed description of the vibrational properties is provided. Unlike other Sillen-type compounds which undergo a tetragonal to collapsed tetragonal pressure-induced phase transition at relatively low pressures, Bi2O2Se shows a remarkable structural stability up to 30 GPa; however, our results indicate that this compound exhibits considerable electronic changes around 4 GPa, likely related to the progressive shortening and hardening of the long and weak Bi-Se bonds linking the Bi2O2 and Se atomic layers. Variations of the structural, vibrational, and electronic properties induced by these electronic changes are discussed.This work was supported by Brazilian Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq) under project 201050/2012-9, by Spanish MINECO projects MAT2015-71070-REDC, MAT2016-75586-C4-1/2/3-P and CTQ2015-65207-P and by the Grant Agency of the Czech Republic (GA CR) under project 16-07711S. Supercomputer time has been provided by the Red Espanola de Supercomputacion (RES) and the MALTA cluster. D.S.-P. and J.A.S. acknowledge the "Ramon y Cajal" fellowship program (RYC-2015-17482) and Spanish Mineco Projects (2014-15643 and 2017-83295-P). J.R.-F. acknowledge the "Juan de la Cierva" program (IJCI-2014-20513) for financial support.Pereira, A.; Santamaría Pérez, D.; Ruiz Fuertes, J.; Manjón, F.; Cuenca Gotor, VP.; Vilaplana Cerda, RI.; Gomis, O.... (2018). Experimental and Theoretical Study of Bi2O2Se Under Compression. The Journal of Physical Chemistry C. 122(16):8853-8867. https://doi.org/10.1021/acs.jpcc.8b02194S885388671221

Characterization and Decomposition of the Natural van der Waals SnSb2Te4 under Compression

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, 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.inorgchem.0c01086.[EN] High pressure X-ray diffraction, Raman scattering, and electrical measurements, together with theoretical calculations, which include the analysis of the topological electron density and electronic localization function, evidence the presence of an isostructural phase transition around 2 GPa, a Fermi resonance around 3.5 GPa, and a pressure-induced decomposition of SnSb2Te4 into the high-pressure phases of its parent binary compounds (alpha-Sb2Te3 and SnTe) above 7 GPa. The internal polyhedral compressibility, the behavior of the Raman-active modes, the electrical behavior, and the nature of its different bonds under compression have been discussed and compared with their parent binary compounds and with related ternary materials. In this context, the Raman spectrum of SnSb2Te4 exhibits vibrational modes that are associated but forbidden in rocksalt-type SnTe; thus showing a novel way to experimentally observe the forbidden vibrational modes of some compounds. Here, some of the bonds are identified with metavalent bonding, which were already observed in their parent binary compounds. The behavior of SnSb2Te4 is framed within the extended orbital radii map of BA(2)Te(4) compounds, so our results pave the way to understand the pressure behavior and stability ranges of other "natural van der Waals" compounds with similar stoichiometry.This work has been performed under financial support from the Spanish MINECO under Project MALTA-CONSOLIDER TEAM network (RED2018-102612-T) and Project FIS2017-83295-P, from Generalitat Valenciana under Project PROMETEO/2018/123. This publication is a product of the "Programa de Valoracion y Recursos Conjuntos de I+D+i VLC/CAMPUS and has been financed by the Spanish Ministerio de Educacion, Cultura y Deporte, as part of "Programa Campus de Excelencia Internacional". Supercomputer time has been provided by the Red Espanola de Supercomputacion (RES) and the MALTA cluster. J.A.S. acknowledges a "Ramon y Cajal" fellowship (RYC-2015-17482) for financial support, and E.L.D.S. acknowledges Marie Sklodowska-Curie Grant No. 785789-COMEX from the European Union's Horizon 2020 research and innovation program. We also thank ALBA synchrotron and DIAMOND light source for funded experiments.Sans-Tresserras, JÁ.; Vilaplana Cerda, RI.; Da Silva, EL.; Popescu, C.; Cuenca-Gotor, VP.; Andrada-Chacón, A.; Sánchez-Benitez, J.... (2020). Characterization and Decomposition of the Natural van der Waals SnSb2Te4 under Compression. Inorganic Chemistry. 59(14):9900-9918. https://doi.org/10.1021/acs.inorgchem.0c01086S990099185914Mellnik, A. R., Lee, J. S., Richardella, A., Grab, J. L., Mintun, P. J., Fischer, M. H., … Ralph, D. C. (2014). Spin-transfer torque generated by a topological insulator. Nature, 511(7510), 449-451. doi:10.1038/nature13534Chen, Y. L., Analytis, J. G., Chu, J.-H., Liu, Z. K., Mo, S.-K., Qi, X. L., … Shen, Z.-X. (2009). Experimental Realization of a Three-Dimensional Topological Insulator, Bi 2 Te 3. Science, 325(5937), 178-181. doi:10.1126/science.1173034Hsieh, D., Xia, Y., Qian, D., Wray, L., Dil, J. H., Meier, F., … Hasan, M. Z. (2009). A tunable topological insulator in the spin helical Dirac transport regime. Nature, 460(7259), 1101-1105. doi:10.1038/nature08234Zhang, T., Jiang, Y., Song, Z., Huang, H., He, Y., Fang, Z., … Fang, C. (2019). Catalogue of topological electronic materials. Nature, 566(7745), 475-479. doi:10.1038/s41586-019-0944-6Vergniory, M. G., Elcoro, L., Felser, C., Regnault, N., Bernevig, B. A., & Wang, Z. (2019). A complete catalogue of high-quality topological materials. Nature, 566(7745), 480-485. doi:10.1038/s41586-019-0954-4Tang, F., Po, H. C., Vishwanath, A., & Wan, X. (2019). Comprehensive search for topological materials using symmetry indicators. Nature, 566(7745), 486-489. doi:10.1038/s41586-019-0937-5Zunger, A. (2019). Beware of plausible predictions of fantasy materials. Nature, 566(7745), 447-449. doi:10.1038/d41586-019-00676-yZhang, H., Liu, C.-X., Qi, X.-L., Dai, X., Fang, Z., & Zhang, S.-C. (2009). Topological insulators in Bi2Se3, Bi2Te3 and Sb2Te3 with a single Dirac cone on the surface. Nature Physics, 5(6), 438-442. doi:10.1038/nphys1270Xia, Y., Qian, D., Hsieh, D., Wray, L., Pal, A., Lin, H., … Hasan, M. Z. (2009). Observation of a large-gap topological-insulator class with a single Dirac cone on the surface. Nature Physics, 5(6), 398-402. doi:10.1038/nphys1274Taherinejad, M., Garrity, K. F., & Vanderbilt, D. (2014). Wannier center sheets in topological insulators. Physical Review B, 89(11). doi:10.1103/physrevb.89.115102Niesner, D., Otto, S., Hermann, V., Fauster, T., Menshchikova, T. V., Eremeev, S. V., … Chulkov, E. V. (2014). Bulk and surface electron dynamics in ap-type topological insulatorSnSb2Te4. Physical Review B, 89(8). doi:10.1103/physrevb.89.081404Venkatasubramanian, R., Siivola, E., Colpitts, T., & O’Quinn, B. (2001). Thin-film thermoelectric devices with high room-temperature figures of merit. Nature, 413(6856), 597-602. doi:10.1038/35098012Eremeev, S. V., Koroteev, Y. M., & Chulkov, E. V. (2010). Effect of the atomic composition of the surface on the electron surface states in topological insulators A 2 V B 3 VI. JETP Letters, 91(8), 387-391. doi:10.1134/s0021364010080059Menshchikova, T. V., Eremeev, S. V., & Chulkov, E. V. (2011). On the origin of two-dimensional electron gas states at the surface of topological insulators. JETP Letters, 94(2), 106-111. doi:10.1134/s0021364011140104Menshchikova, T. V., Eremeev, S. V., & Chulkov, E. V. (2013). Electronic structure of SnSb2Te4 and PbSb2Te4 topological insulators. Applied Surface Science, 267, 1-3. doi:10.1016/j.apsusc.2012.04.048Concas, G., de Pascale, T. M., Garbato, L., Ledda, F., Meloni, F., Rucci, A., & Serra, M. (1992). Electronic and structural properties of the layered SnSb2Te4 semiconductor: Ab initio total-energy and Mössbauer spectroscopy study. Journal of Physics and Chemistry of Solids, 53(6), 791-796. doi:10.1016/0022-3697(92)90191-fEremeev, S. V., Menshchikova, T. V., Silkin, I. V., Vergniory, M. G., Echenique, P. M., & Chulkov, E. V. (2015). Sublattice effect on topological surface states in complex(SnTe)n>1(Bi2Te3)m=1compounds. Physical Review B, 91(24). doi:10.1103/physrevb.91.245145Kuznetsov, A. Y., Pereira, A. S., Shiryaev, A. A., Haines, J., Dubrovinsky, L., Dmitriev, V., … Guignot, N. (2006). Pressure-Induced Chemical Decomposition and Structural Changes of Boric Acid. The Journal of Physical Chemistry B, 110(28), 13858-13865. doi:10.1021/jp061650dShelimova, L. E., Karpinskii, O. G., Konstantinov, P. P., Avilov, E. S., Kretova, M. A., & Zemskov, V. S. (2004). Crystal Structures and Thermoelectric Properties of Layered Compounds in the ATe–Bi2Te3(A = Ge, Sn, Pb) Systems. Inorganic Materials, 40(5), 451-460. doi:10.1023/b:inma.0000027590.43038.a8Kuropatwa, B. A., Assoud, A., & Kleinke, H. (2013). Effects of Cation Site Substitutions on the Thermoelectric Performance of Layered SnBi2Te4utilizing the Triel Elements Ga, In, and Tl. Zeitschrift für anorganische und allgemeine Chemie, 639(14), 2411-2420. doi:10.1002/zaac.201300325Kuropatwa, B. A., & Kleinke, H. (2012). Thermoelectric Properties of Stoichiometric Compounds in the (SnTe)x(Bi2Te3)ySystem. Zeitschrift für anorganische und allgemeine Chemie, 638(15), 2640-2647. doi:10.1002/zaac.201200284Banik, A., & Biswas, K. (2017). Synthetic Nanosheets of Natural van der Waals Heterostructures. Angewandte Chemie International Edition, 56(46), 14561-14566. doi:10.1002/anie.201708293Shelimova, L. E., Karpinskii, O. G., Svechnikova, T. E., Nikhezina, I. Y., Avilov, E. S., Kretova, M. A., & Zemskov, V. S. (2008). Effect of cadmium, silver, and tellurium doping on the properties of single crystals of the layered compounds PbBi4Te7 and PbSb2Te4. Inorganic Materials, 44(4), 371-376. doi:10.1134/s0020168508040080Shu, H. W., Jaulmes, S., & Flahaut, J. (1988). Syste`me AsGeTe. Journal of Solid State Chemistry, 74(2), 277-286. doi:10.1016/0022-4596(88)90356-8Adouby, K., Abba Touré, A., Kra, G., Olivier-Fourcade, J., Jumas, J.-C., & Perez Vicente, C. (2000). Phase diagram and local environment of Sn and Te: SnTe Bi and SnTe Bi 2 Te 3 systems. Comptes Rendus de l’Académie des Sciences - Series IIC - Chemistry, 3(1), 51-58. doi:10.1016/s1387-1609(00)00105-5Oeckler, O., Schneider, M. N., Fahrnbauer, F., & Vaughan, G. (2011). Atom distribution in SnSb2Te4 by resonant X-ray diffraction. Solid State Sciences, 13(5), 1157-1161. doi:10.1016/j.solidstatesciences.2010.12.043Schäfer, T., Konze, P. M., Huyeng, J. D., Deringer, V. L., Lesieur, T., Müller, P., … Wuttig, M. (2017). Chemical Tuning of Carrier Type and Concentration in a Homologous Series of Crystalline Chalcogenides. Chemistry of Materials, 29(16), 6749-6757. doi:10.1021/acs.chemmater.7b01595Gallus, J. Lattice Dynamics in the SnSb2Te4 Phase Change Material. Diplomarbeit; Rheinisch-Westfälischen Technischen Hochschule Aachen: 2011.Wuttig, M., Deringer, V. L., Gonze, X., Bichara, C., & Raty, J.-Y. (2018). Incipient Metals: Functional Materials with a Unique Bonding Mechanism. Advanced Materials, 30(51), 1803777. doi:10.1002/adma.201803777Raty, J., Schumacher, M., Golub, P., Deringer, V. L., Gatti, C., & Wuttig, M. (2018). A Quantum‐Mechanical Map for Bonding and Properties in Solids. Advanced Materials, 31(3), 1806280. doi:10.1002/adma.201806280Yu, Y., Cagnoni, M., Cojocaru‐Mirédin, O., & Wuttig, M. (2019). Chalcogenide Thermoelectrics Empowered by an Unconventional Bonding Mechanism. Advanced Functional Materials, 30(8), 1904862. doi:10.1002/adfm.201904862Cheng, Y., Cojocaru‐Mirédin, O., Keutgen, J., Yu, Y., Küpers, M., Schumacher, M., … Wuttig, M. (2019). Understanding the Structure and Properties of Sesqui‐Chalcogenides (i.e., V 2 VI 3 or Pn 2 Ch 3 (Pn = Pnictogen, Ch = Chalcogen) Compounds) from a Bonding Perspective. Advanced Materials, 31(43), 1904316. doi:10.1002/adma.201904316Kooi, B. J., & Wuttig, M. (2020). Chalcogenides by Design: Functionality through Metavalent Bonding and Confinement. Advanced Materials, 32(21), 1908302. doi:10.1002/adma.201908302Hsieh, W.-P., Zalden, P., Wuttig, M., Lindenberg, A. M., & Mao, W. L. (2013). High-pressure Raman spectroscopy of phase change materials. Applied Physics Letters, 103(19), 191908. doi:10.1063/1.4829358Vilaplana, R., Sans, J. A., Manjón, F. J., Andrada-Chacón, A., Sánchez-Benítez, J., Popescu, C., … Oeckler, O. (2016). Structural and electrical study of the topological insulator SnBi2Te4 at high pressure. Journal of Alloys and Compounds, 685, 962-970. doi:10.1016/j.jallcom.2016.06.170Song, P., Matsumoto, R., Hou, Z., Adachi, S., Hara, H., Saito, Y., … Takano, Y. (2020). Pressure-induced superconductivity in SnSb2Te4. Journal of Physics: Condensed Matter, 32(23), 235901. doi:10.1088/1361-648x/ab76e2Fauth, F., Peral, I., Popescu, C., & Knapp, M. (2013). The new Material Science Powder Diffraction beamline at ALBA Synchrotron. Powder Diffraction, 28(S2), S360-S370. doi:10.1017/s0885715613000900Dewaele, A., Loubeyre, P., & Mezouar, M. (2004). Equations of state of six metals above94GPa. Physical Review B, 70(9). doi:10.1103/physrevb.70.094112Hammersley, A. P., Svensson, S. O., Hanfland, M., Fitch, A. N., & Hausermann, D. (1996). Two-dimensional detector software: From real detector to idealised image or two-theta scan. High Pressure Research, 14(4-6), 235-248. doi:10.1080/08957959608201408Toby, B. H. (2001). EXPGUI, a graphical user interface forGSAS. Journal of Applied Crystallography, 34(2), 210-213. doi:10.1107/s0021889801002242Larson, A. C.; Von Dreele, R. B.General Structure Analysis System (GSAS). Los Alamos National Laboratory Report LAUR 86-748; 1994.Klotz, S., Chervin, J.-C., Munsch, P., & Le Marchand, G. (2009). Hydrostatic limits of 11 pressure transmitting media. Journal of Physics D: Applied Physics, 42(7), 075413. doi:10.1088/0022-3727/42/7/075413Errandonea, D., Muñoz, A., & Gonzalez-Platas, J. (2014). Comment on «High-pressure x-ray diffraction study of YBO3/Eu3+, GdBO3, and EuBO3: Pressure-induced amorphization in GdBO3» [J. Appl. Phys. 115, 043507 (2014)]. Journal of Applied Physics, 115(21), 216101. doi:10.1063/1.4881057Mao, H. K., Xu, J., & Bell, P. M. (1986). Calibration of the ruby pressure gauge to 800 kbar under quasi-hydrostatic conditions. Journal of Geophysical Research, 91(B5), 4673. doi:10.1029/jb091ib05p04673Syassen, K. (2008). Ruby under pressure. High Pressure Research, 28(2), 75-126. doi:10.1080/08957950802235640Debernardi, A., Ulrich, C., Cardona, M., & Syassen, K. (2001). Pressure Dependence of Raman Linewidth in Semiconductors. physica status solidi (b), 223(1), 213-223. doi:10.1002/1521-3951(200101)223:13.0.co;2-iGarcia-Domene, B., Ortiz, H. M., Gomis, O., Sans, J. A., Manjón, F. J., Muñoz, A., … Tyagi, A. K. (2012). High-pressure lattice dynamical study of bulk and nanocrystalline In2O3. Journal of Applied Physics, 112(12), 123511. doi:10.1063/1.4769747Hohenberg, P., & Kohn, W. (1964). Inhomogeneous Electron Gas. Physical Review, 136(3B), B864-B871. doi:10.1103/physrev.136.b864Blöchl, P. E. (1994). Projector augmented-wave method. Physical Review B, 50(24), 17953-17979. doi:10.1103/physrevb.50.17953Kresse, G., & Hafner, J. (1993). Ab initiomolecular dynamics for liquid metals. Physical Review B, 47(1), 558-561. doi:10.1103/physrevb.47.558Perdew, J. P., Ruzsinszky, A., Csonka, G. I., Vydrov, O. A., Scuseria, G. E., Constantin, L. A., … Burke, K. (2008). Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces. Physical Review Letters, 100(13). doi:10.1103/physrevlett.100.136406Mujica, A., Rubio, A., Muñoz, A., & Needs, R. J. (2003). High-pressure phases of group-IV, III–V, and II–VI compounds. Reviews of Modern Physics, 75(3), 863-912. doi:10.1103/revmodphys.75.863Parlinski, K. see: http://www.computingformaterials.com/index.html. March 2020.Tang, W., Sanville, E., & Henkelman, G. (2009). A grid-based Bader analysis algorithm without lattice bias. Journal of Physics: Condensed Matter, 21(8), 084204. doi:10.1088/0953-8984/21/8/084204Sanville, E., Kenny, S. D., Smith, R., & Henkelman, G. (2007). Improved grid-based algorithm for Bader charge allocation. Journal of Computational Chemistry, 28(5), 899-908. doi:10.1002/jcc.20575Henkelman, G., Arnaldsson, A., & Jónsson, H. (2006). A fast and robust algorithm for Bader decomposition of charge density. Computational Materials Science, 36(3), 354-360. doi:10.1016/j.commatsci.2005.04.010Yu, M., & Trinkle, D. R. (2011). Accurate and efficient algorithm for Bader charge integration. The Journal of Chemical Physics, 134(6), 064111. doi:10.1063/1.3553716http://theory.cm.utexas.edu/henkelman/code/bader/. March 2019.Johnson, E. R., Keinan, S., Mori-Sánchez, P., Contreras-García, J., Cohen, A. J., & Yang, W. (2010). Revealing Noncovalent Interactions. Journal of the American Chemical Society, 132(18), 6498-6506. doi:10.1021/ja100936wContreras-García, J., Johnson, E. R., Keinan, S., Chaudret, R., Piquemal, J.-P., Beratan, D. N., & Yang, W. (2011). NCIPLOT: A Program for Plotting Noncovalent Interaction Regions. Journal of Chemical Theory and Computation, 7(3), 625-632. doi:10.1021/ct100641aAngel, R. J., Alvaro, M., & Gonzalez-Platas, J. (2014). EosFit7c and a Fortran module (library) for equation of state calculations. Zeitschrift für Kristallographie - Crystalline Materials, 229(5), 405-419. doi:10.1515/zkri-2013-1711Zhou, D., Li, Q., Ma, Y., Cui, Q., & Chen, C. (2013). Unraveling Convoluted Structural Transitions in SnTe at High Pressure. The Journal of Physical Chemistry C, 117(10), 5352-5357. doi:10.1021/jp4008762Gomis, O., Vilaplana, R., Manjón, F. J., Rodríguez-Hernández, P., Pérez-González, E., Muñoz, A., … Drasar, C. (2011). Lattice dynamics of Sb2Te3at high pressures. Physical Review B, 84(17). doi:10.1103/physrevb.84.174305Sakai, N., Kajiwara, T., Takemura, K., Minomura, S., & Fujii, Y. (1981). Pressure-induced phase transition in Sb2Te3. Solid State Communications, 40(12), 1045-1047. doi:10.1016/0038-1098(81)90248-9Wang, B.-T., Souvatzis, P., Eriksson, O., & Zhang, P. (2015). Lattice dynamics and chemical bonding in Sb2Te3 from first-principles calculations. The Journal of Chemical Physics, 142(17), 174702. doi:10.1063/1.4919683Pereira, A. L. J., Sans, J. A., Vilaplana, R., Gomis, O., Manjón, F. J., Rodríguez-Hernández, P., … Beltrán, A. (2014). Isostructural Second-Order Phase Transition of β-Bi2O3 at High Pressures: An Experimental and Theoretical Study. The Journal of Physical Chemistry C, 118(40), 23189-23201. doi:10.1021/jp507826jCuenca-Gotor, V. P., Sans, J. A., Ibáñez, J., Popescu, C., Gomis, O., Vilaplana, R., … Bergara, A. (2016). Structural, Vibrational, and Electronic Study of α-As2Te3 under Compression. The Journal of Physical Chemistry C, 120(34), 19340-19352. doi:10.1021/acs.jpcc.6b06049Robinson, K., Gibbs, G. V., & Ribbe, P. H. (1971). Quadratic Elongation: A Quantitative Measure of Distortion in Coordination Polyhedra. Science, 172(3983), 567-570. doi:10.1126/science.172.3983.567Baur, W. H. (1974). The geometry of polyhedral distortions. Predictive relationships for the phosphate group. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, 30(5), 1195-1215. doi:10.1107/s0567740874004560Walsh, A., & Watson, G. W. (2005). Influence of the Anion on Lone Pair Formation in Sn(II) Monochalcogenides:  A DFT Study. The Journal of Physical Chemistry B, 109(40), 18868-18875. doi:10.1021/jp051822rSkowron, A., Boswell, F. W., Corbett, J. M., & Taylor, N. J. (1994). Structure Determination of PbSb2Se4. Journal of Solid State Chemistry, 112(2), 251-254. doi:10.1006/jssc.1994.1300Smith, P. P. K., & Parise, J. B. (1985). Structure determination of SnSb2S4 and SnSb2Se4 by high-resolution electron microscopy. Acta Crystallographica Section B Structural Science, 41(2), 84-87. doi:10.1107/s0108768185001665Iitaka, Y., & Nowacki, W. (1962). A redetermination of the crystal structure of galenobismutite, PbBi2S4. Acta Crystallographica, 15(7), 691-698. doi:10.1107/s0365110x62001887Gaspard, J.-P., & Ceolin, R. (1992). Hume-Rothery rule in V–VI compounds. Solid State Communications, 84(8), 839-842. doi:10.1016/0038-1098(92)90102-fGaspard, J.-P., Pellegatti, A., Marinelli, F., & Bichara, C. (1998). Peierls instabilities in covalent structures I. Electronic structure, cohesion and theZ= 8 –Nrule. Philosophical Magazine B, 77(3), 727-744. doi:10.1080/13642819808214831Seo, D.-K., & Hoffmann, R. (1999). What Determines the Structures of the Group 15 Elements? Journal of Solid State Chemistry, 147(1), 26-37. doi:10.1006/jssc.1999.8140Zhang, H., Liu, C.-X., & Zhang, S.-C. (2013). Spin-Orbital Texture in Topological Insulators. Physical Review Letters, 111(6). doi:10.1103/physrevlett.111.066801Tamtögl, A., Kraus, P., Mayrhofer-Reinhartshuber, M., Benedek, G., Bernasconi, M., Dragoni, D., … Ernst, W. E. (2019). Statics and dynamics of multivalley charge density waves in Sb(111). npj Quantum Materials, 4(1). doi:10.1038/s41535-019-0168-xLi, Y.; Parsons, C.; Ramakrishna, S.; Dwivedi, A.; Schofield, M.; Reyes, A.; Guptasarma, P. Charge Density Wave Order in the Topological Insulator Bi2Se3. arXiv: 2002.12546.Boulfelfel, S. E., Seifert, G., Grin, Y., & Leoni, S. (2012). Squeezing lone pairs: TheA17 toA7 pressure-induced phase transition in black phosphorus. Physical Review B, 85(1). doi:10.1103/physrevb.85.014110Zhang, X., Stevanović, V., d’ Avezac, M., Lany, S., & Zunger, A. (2012). Prediction ofA2BX4metal-chalcogenide compounds via first-principles thermodynamics. Physical Review B, 86(1). doi:10.1103/physrevb.86.014109Zunger, A. (1980). Systematization of the stable crystal structure of allAB-type binary compounds: A pseudopotential orbital-radii approach. Physical Review B, 22(12), 5839-5872. doi:10.1103/physrevb.22.5839Manjón, F. J., Vilaplana, R., Gomis, O., Pérez-González, E., Santamaría-Pérez, D., Marín-Borrás, V., … Muñoz-Sanjosé, V. (2013). High-pressure studies of topological insulators Bi2Se3, Bi2Te3, and Sb2Te3. physica status solidi (b), 250(4), 669-676. doi:10.1002/pssb.201200672Kolobov, A. V., Haines, J., Pradel, A., Ribes, M., Fons, P., Tominaga, J., … Uruga, T. (2006). Pressure-Induced Site-Selective Disordering ofGe2Sb2Te5: A New Insight into Phase-Change Optical Recording. Physical Review Letters, 97(3). doi:10.1103/physrevlett.97.035701Arora, A. . (2000). Pressure-induced amorphization versus decomposition. Solid State Communications, 115(12), 665-668. doi:10.1016/s0038-1098(00)00253-2Bassett, W. A., & Li-Chung Ming. (1972). Disproportionation of Fe2SiO4 to 2FeO+SiO2 at pressures up to 250kbar and temperatures up to 3000 °C. Physics of the Earth and Planetary Interiors, 6(1-3), 154-160. doi:10.1016/0031-9201(72)90048-9Fei, Y., & Mao, H.-K. (1993). Static compression of Mg(OH)2to 78 GPa at high temperature and constraints on the equation of state of fluid H2O. Journal of Geophysical Research: Solid Earth, 98(B7), 11875-11884. doi:10.1029/93jb00701Kuznetsov, A. Y., Pereira, A. S., Shiryaev, A. A., Haines, J., Dubrovinsky, L., Dmitriev, V., … Guignot, N. (2006). Pressure-Induced Chemical Decomposition and Structural Changes of Boric Acid. The Journal of Physical Chemistry B, 110(28), 13858-13865. doi:10.1021/jp061650dCatafesta, J., Rovani, P. R., Perottoni, C. A., & Pereira, A. S. (2015). Pressure-enhanced decomposition of Ag3[Co(CN)6]. Journal of Physics and

Structural, vibrational and electrical study of compressed BiTeBr

Compresed BiTeBr has been studied from a joint experimental and theoretical perspective. Room-temperature x-ray diffraction, Raman scattering, and transport measurements at high pressures have been performed in this layered semiconductor and interpreted with the help of ab initio calculations. A reversible first-order phase transition has been observed above 6–7 GPa, but changes in structural, vibrational, and electrical properties have also been noted near 2 GPa. Structural and vibrational changes are likely due to the hardening of interlayer forces rather than to a second-order isostructural phase transition while electrical changes are mainly attributed to changes in the electron mobility. The possibility of a pressure-induced electronic topological transition and of a pressure-induced quantum topological phase transition in BiTeBr and other bismuth tellurohalides, like BiTeI, is also discussed.This work has been performed under financial support from Spanish MINECO under Projects No. MAT2013-46649-C4-2/3-P and MAT2015-71070-REDC. This publication is the outcome of "Programa de Valoracion y Recursos Conjuntos de I+D+i VLC/CAMPUS" and has been financed by the Spanish Ministerio de Educacion, Cultura y Deporte as part of "Programa Campus de Excelencia Internacional" through Projects No. SP20140701 and No. SP20140871. Supercomputer time has been provided by the Red Espanola de Supercomputacion (RES) and the MALTA cluster. J.A.S. acknowledges the "Juan de la Cierva" fellowship program for financial support.Sans-Tresserras, JÁ.; Manjón Herrera, FJ.; Pereira, A.; Vilaplana Cerda, RI.; Gomis, O.; Segura, A.; Muñoz, A.... (2016). Structural, vibrational and electrical study of compressed BiTeBr. Physical review B: Condensed matter and materials physics. 93:024110-1-024110-11. https://doi.org/10.1103/PhysRevB.93.024110S024110-1024110-1193Ishizaka, K., Bahramy, M. S., Murakawa, H., Sakano, M., Shimojima, T., Sonobe, T., … Tokura, Y. (2011). Giant Rashba-type spin splitting in bulk BiTeI. Nature Materials, 10(7), 521-526. doi:10.1038/nmat3051Crepaldi, A., Moreschini, L., Autès, G., Tournier-Colletta, C., Moser, S., Virk, N., … Grioni, M. (2012). Giant Ambipolar Rashba Effect in the Semiconductor BiTeI. Physical Review Letters, 109(9). doi:10.1103/physrevlett.109.096803Landolt, G., Eremeev, S. V., Koroteev, Y. M., Slomski, B., Muff, S., Neupert, T., … Dil, J. H. (2012). Disentanglement of Surface and Bulk Rashba Spin Splittings in Noncentrosymmetric BiTeI. Physical Review Letters, 109(11). doi:10.1103/physrevlett.109.116403Sakano, M., Bahramy, M. S., Katayama, A., Shimojima, T., Murakawa, H., Kaneko, Y., … Ishizaka, K. (2013). Strongly Spin-Orbit Coupled Two-Dimensional Electron Gas Emerging near the Surface of Polar Semiconductors. Physical Review Letters, 110(10). doi:10.1103/physrevlett.110.107204Chen, Y. L., Kanou, M., Liu, Z. K., Zhang, H. J., Sobota, J. A., Leuenberger, D., … Sasagawa, T. (2013). Discovery of a single topological Dirac fermion in the strong inversion asymmetric compound BiTeCl. Nature Physics, 9(11), 704-708. doi:10.1038/nphys2768Xiang, F.-X., Wang, X.-L., Veldhorst, M., Dou, S.-X., & Fuhrer, M. S. (2015). Observation of topological transition of Fermi surface from a spindle torus to a torus in bulk Rashba spin-split BiTeCl. Physical Review B, 92(3). doi:10.1103/physrevb.92.035123Bahramy, M. S., Arita, R., & Nagaosa, N. (2011). Origin of giant bulk Rashba splitting: Application to BiTeI. Physical Review B, 84(4). doi:10.1103/physrevb.84.041202Eremeev, S. V., Nechaev, I. A., & Chulkov, E. V. (2012). Giant Rashba-type spin splitting at polar surfaces of BiTeI. JETP Letters, 96(7), 437-444. doi:10.1134/s0021364012190071Zhu, Z., Cheng, Y., & Schwingenschlögl, U. (2013). Orbital-dependent Rashba coupling in bulk BiTeCl and BiTeI. New Journal of Physics, 15(2), 023010. doi:10.1088/1367-2630/15/2/023010Nayak, C., Simon, S. H., Stern, A., Freedman, M., & Das Sarma, S. (2008). Non-Abelian anyons and topological quantum computation. Reviews of Modern Physics, 80(3), 1083-1159. doi:10.1103/revmodphys.80.1083Alicea, J., Oreg, Y., Refael, G., von Oppen, F., & Fisher, M. P. A. (2011). Non-Abelian statistics and topological quantum information processing in 1D wire networks. Nature Physics, 7(5), 412-417. doi:10.1038/nphys1915Bahramy, M. S., Yang, B.-J., Arita, R., & Nagaosa, N. (2012). Emergence of non-centrosymmetric topological insulating phase in BiTeI under pressure. Nature Communications, 3(1). doi:10.1038/ncomms1679Xi, X., Ma, C., Liu, Z., Chen, Z., Ku, W., Berger, H., … Carr, G. L. (2013). Signatures of a Pressure-Induced Topological Quantum Phase Transition in BiTeI. Physical Review Letters, 111(15). doi:10.1103/physrevlett.111.155701Ponosov, Y. S., Kuznetsova, T. V., Tereshchenko, O. E., Kokh, K. A., & Chulkov, E. V. (2014). Dynamics of the BiTeI lattice at high pressures. JETP Letters, 98(9), 557-561. doi:10.1134/s0021364013220074Tran, M. K., Levallois, J., Lerch, P., Teyssier, J., Kuzmenko, A. B., Autès, G., … Akrap, A. (2014). Infrared- and Raman-Spectroscopy Measurements of a Transition in the Crystal Structure and a Closing of the Energy Gap of BiTeI under Pressure. Physical Review Letters, 112(4). doi:10.1103/physrevlett.112.047402Rusinov, I. P., Nechaev, I. A., Eremeev, S. V., Friedrich, C., Blügel, S., & Chulkov, E. V. (2013). Many-body effects on the Rashba-type spin splitting in bulk bismuth tellurohalides. Physical Review B, 87(20). doi:10.1103/physrevb.87.205103Chen, Y., Xi, X., Yim, W.-L., Peng, F., Wang, Y., Wang, H., … Berger, H. (2013). High-Pressure Phase Transitions and Structures of Topological Insulator BiTeI. The Journal of Physical Chemistry C, 117(48), 25677-25683. doi:10.1021/jp409824gD�nges, E. (1951). �ber Chalkogenohalogenide des dreiwertigen Antimons und Wismuts. III. �ber Tellurohalogenide des dreiwertigen Antimons und Wismuts und �ber Antimon-und Wismut(III)-tellurid und Wismut(III)-selenid. Zeitschrift f�r anorganische und allgemeine Chemie, 265(1-3), 56-61. doi:10.1002/zaac.19512650106Shevelkov, A. V., Dikarev, E. V., Shpanchenko, R. V., & Popovkin, B. A. (1995). Crystal Structures of Bismuth Tellurohalides BiTeX (X = Cl, Br, I) from X-Ray Powder Diffraction Data. Journal of Solid State Chemistry, 114(2), 379-384. doi:10.1006/jssc.1995.1058Eremeev, S. V., Rusinov, I. P., Nechaev, I. A., & Chulkov, E. V. (2013). Rashba split surface states in BiTeBr. New Journal of Physics, 15(7), 075015. doi:10.1088/1367-2630/15/7/075015Akrap, A., Teyssier, J., Magrez, A., Bugnon, P., Berger, H., Kuzmenko, A. B., & van der Marel, D. (2014). Optical properties of BiTeBr and BiTeCl. Physical Review B, 90(3). doi:10.1103/physrevb.90.035201Kulbachinskii, V. A., Kytin, V. G., Lavrukhina, Z. V., Kuznetsov, A. N., & Shevelkov, A. V. (2010). Galvanomagnetic and thermoelectric properties of BiTeBr and BiTeI single crystals and their electronic structure. Semiconductors, 44(12), 1548-1553. doi:10.1134/s1063782610120031Kulbachinskii, V. A., Kytin, V. G., Kudryashov, A. A., Kuznetsov, A. N., & Shevelkov, A. V. (2012). On the electronic structure and thermoelectric properties of BiTeBr and BiTeI single crystals and of BiTeI with the addition of BiI3 and CuI. Journal of Solid State Chemistry, 193, 154-160. doi:10.1016/j.jssc.2012.05.037Ma, Y., Dai, Y., Wei, W., Li, X., & Huang, B. (2014). Emergence of electric polarity in BiTeX (X = Br and I) monolayers and the giant Rashba spin splitting. Physical Chemistry Chemical Physics, 16(33), 17603. doi:10.1039/c4cp01975jMatyáš, M., Horák, J., & Klubíčková, B. (1980). Some physical properties of n-type BiTeBr single crystals. Physica Status Solidi (a), 61(2), 419-423. doi:10.1002/pssa.2210610212Fauth, F., Peral, I., Popescu, C., & Knapp, M. (2013). The new Material Science Powder Diffraction beamline at ALBA Synchrotron. Powder Diffraction, 28(S2), S360-S370. doi:10.1017/s0885715613000900Hammersley, A. P., Svensson, S. O., Hanfland, M., Fitch, A. N., & Hausermann, D. (1996). Two-dimensional detector software: From real detector to idealised image or two-theta scan. High Pressure Research, 14(4-6), 235-248. doi:10.1080/08957959608201408Toby, B. H. (2001). EXPGUI, a graphical user interface forGSAS. Journal of Applied Crystallography, 34(2), 210-213. doi:10.1107/s0021889801002242Momma, K., & Izumi, F. (2011). VESTA 3for three-dimensional visualization of crystal, volumetric and morphology data. Journal of Applied Crystallography, 44(6), 1272-1276. doi:10.1107/s0021889811038970Dewaele, A., Loubeyre, P., & Mezouar, M. (2004). Equations of state of six metals above94GPa. Physical Review B, 70(9). doi:10.1103/physrevb.70.094112Piermarini, G. J., Block, S., & Barnett, J. D. (1973). Hydrostatic limits in liquids and solids to 100 kbar. Journal of Applied Physics, 44(12), 5377-5382. doi:10.1063/1.1662159Errandonea, D., Meng, Y., Somayazulu, M., & Häusermann, D. (2005). Pressure-induced transition in titanium metal: a systematic study of the effects of uniaxial stress. Physica B: Condensed Matter, 355(1-4), 116-125. doi:10.1016/j.physb.2004.10.030Syassen, K. (2008). Ruby under pressure. High Pressure Research, 28(2), 75-126. doi:10.1080/08957950802235640Errandonea, D., Segura, A., Martínez-García, D., & Muñoz-San Jose, V. (2009). Hall-effect and resistivity measurements in CdTe and ZnTe at high pressure: Electronic structure of impurities in the zinc-blende phase and the semimetallic or metallic character of the high-pressure phases. Physical Review B, 79(12). doi:10.1103/physrevb.79.125203Errandonea, D., Martínez-García, D., Segura, A., Ruiz-Fuertes, J., Lacomba-Perales, R., Fages, V., … Mũnoz-San José, V. (2006). High-pressure electrical transport measurements on p-type GaSe and InSe. High Pressure Research, 26(4), 513-516. doi:10.1080/08957950601101787Hohenberg, P., & Kohn, W. (1964). Inhomogeneous Electron Gas. Physical Review, 136(3B), B864-B871. doi:10.1103/physrev.136.b864Kresse, G., & Hafner, J. (1993). Ab initiomolecular dynamics for liquid metals. Physical Review B, 47(1), 558-561. doi:10.1103/physrevb.47.558Kresse, G., & Hafner, J. (1994). Ab initiomolecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Physical Review B, 49(20), 14251-14269. doi:10.1103/physrevb.49.14251Kresse, G., & Furthmüller, J. (1996). Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Computational Materials Science, 6(1), 15-50. doi:10.1016/0927-0256(96)00008-0Kresse, G., & Furthmüller, J. (1996). Efficient iterative schemes forab initiototal-energy calculations using a plane-wave basis set. Physical Review B, 54(16), 11169-11186. doi:10.1103/physrevb.54.11169Blöchl, P. E. (1994). Projector augmented-wave method. Physical Review B, 50(24), 17953-17979. doi:10.1103/physrevb.50.17953Kresse, G., & Joubert, D. (1999). From ultrasoft pseudopotentials to the projector augmented-wave method. Physical Review B, 59(3), 1758-1775. doi:10.1103/physrevb.59.1758Perdew, J. P., Ruzsinszky, A., Csonka, G. I., Vydrov, O. A., Scuseria, G. E., Constantin, L. A., … Burke, K. (2008). Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces. Physical Review Letters, 100(13). doi:10.1103/physrevlett.100.136406Mujica, A., Rubio, A., Muñoz, A., & Needs, R. J. (2003). High-pressure phases of group-IV, III–V, and II–VI compounds. Reviews of Modern Physics, 75(3), 863-912. doi:10.1103/revmodphys.75.863Kroumova, E., Aroyo, M. I., Perez-Mato, J. M., Kirov, A., Capillas, C., Ivantchev, S., & Wondratschek, H. (2003). Bilbao Crystallographic Server : Useful Databases and Tools for Phase-Transition Studies. Phase Transitions, 76(1-2), 155-170. doi:10.1080/0141159031000076110Pereira, A. L. J., Gracia, L., Santamaría-Pérez, D., Vilaplana, R., Manjón, F. J., Errandonea, D., … Beltrán, A. (2012). Structural and vibrational study of cubic Sb2O3under high pressure. Physical Review B, 85(17). doi:10.1103/physrevb.85.174108Pereira, A. L. J., Sans, J. A., Vilaplana, R., Gomis, O., Manjón, F. J., Rodríguez-Hernández, P., … Beltrán, A. (2014). Isostructural Second-Order Phase Transition of β-Bi2O3 at High Pressures: An Experimental and Theoretical Study. The Journal of Physical Chemistry C, 118(40), 23189-23201. doi:10.1021/jp507826jVilaplana, R., Gomis, O., Manjón, F. J., Segura, A., Pérez-González, E., Rodríguez-Hernández, P., … Kucek, V. (2011). High-pressure vibrational and optical study of Bi2Te3. Physical Review B, 84(10). doi:10.1103/physrevb.84.104112Gomis, O., Vilaplana, R., Manjón, F. J., Rodríguez-Hernández, P., Pérez-González, E., Muñoz, A., … Drasar, C. (2011). Lattice dynamics of Sb2Te3at high pressures. Physical Review B, 84(17). doi:10.1103/physrevb.84.174305Vilaplana, R., Santamaría-Pérez, D., Gomis, O., Manjón, F. J., González, J., Segura, A., … Kucek, V. (2011). Structural and vibrational study of Bi2Se3under high pressure. Physical Review B, 84(18). doi:10.1103/physrevb.84.184110Moreschini, L., Autès, G., Crepaldi, A., Moser, S., Johannsen, J. C., Kim, K. S., … Grioni, M. (2015). Bulk and surface band structure of the new family of semiconductors BiTeX (X=I, Br, Cl). Journal of Electron Spectroscopy and Related Phenomena, 201, 115-120. doi:10.1016/j.elspec.2014.11.004VanGennep, D., Maiti, S., Graf, D., Tozer, S. W., Martin, C., Berger, H., … Hamlin, J. J. (2014). Pressure tuning the Fermi level through the Dirac point of giant Rashba semiconductor BiTeI. Journal of Physics: Condensed Matter, 26(34), 342202. doi:10.1088/0953-8984/26/34/342202Ideue, T., Checkelsky, J. G., Bahramy, M. S., Murakawa, H., Kaneko, Y., Nagaosa, N., & Tokura, Y. (2014). Pressure variation of Rashba spin splitting toward topological transition in the polar semiconductor BiTeI. Physical Review B, 90(16). doi:10.1103/physrevb.90.161107Wu, L., Yang, J., Wang, S., Wei, P., Yang, J., Zhang, W., & Chen, L. (2014). Two-dimensional thermoelectrics with Rashba spin-split bands in bulk BiTeI. Physical Review B, 90(19). doi:10.1103/physrevb.90.195210Errandonea, D., Segura, A., Manjón, F. J., Chevy, A., Machado, E., Tobias, G., … Canadell, E. (2005). Crystal symmetry and pressure effects on the valence band structure ofγ-InSe andε-GaSe: Transport measurements and electronic structure calculations. Physical Review B, 71(12). doi:10.1103/physrevb.71.12520

High-pressure structural and elastic properties of Tl2O3

The structural properties of Thallium (III) oxide (Tl2O3) have been studied both experimentally and theoretically under compression at room temperature. X-ray powder diffraction measurements up to 37.7 GPa have been complemented with ab initio total-energy calculations. The equation of state of Tl2O3 has been determined and compared to related compounds. It has been found experimentally that Tl2O3 remains in its initial cubic bixbyite-type structure up to 22.0 GPa. At this pressure, the onset of amorphization is observed, being the sample fully amorphous at 25.2 GPa. The sample retains the amorphous state after pressure release. To understand the pressure-induced amorphization process, we have studied theoretically the possible high-pressure phases of Tl2O3. Although a phase transition is theoretically predicted at 5.8 GPa to the orthorhombic Rh2O3-II-type structure and at 24.2 GPa to the orthorhombic alpha-Gd2S3-type structure, neither of these phases were observed experimentally, probably due to the hindrance of the pressure-driven phase transitions at room temperature. The theoretical study of the elastic behavior of the cubic bixbyite-type structure at high-pressure shows that amorphization above 22 GPa at room temperature might be caused by the mechanical instability of the cubic bixbyite-type structure which is theoretically predicted above 23.5 GPa. (C) 2014 AIP Publishing LLC.This study was supported by the Spanish government MEC under Grant Nos. MAT2010-21270-C04-01/03/04, MAT2013-46649-C4-1/2/3-P, and CTQ2009-14596-C02-01, by the Comunidad de Madrid and European Social Fund (S2009/PPQ-1551 4161893), by MALTA Consolider Ingenio 2010 project (CSD2007-00045), and by Generalitat Valenciana (GVA-ACOMP-2013-1012 and GVA-ACOMP-2014-243). We acknowledge Diamond Light Source for time on beamline I15 under proposal EE6517 and I15 beamline scientist for technical support. A.M. and P.R.-H. acknowledge computing time provided by Red Espanola de Supercomputacion (RES) and MALTA-Cluster. B.G.-D. and J.A.S. acknowledge financial support through the FPI program and Juan de la Cierva fellowship. J.R.-F. acknowledges the Alexander von Humboldt Foundation for a postdoctoral fellowship.Gomis, O.; Santamaría-Pérez, D.; Ruiz-Fuertes, J.; Sans, JA.; Vilaplana Cerda, RI.; Ortiz, HM.; García-Domene, B.... (2014). High-pressure structural and elastic properties of Tl2O3. Journal of Applied Physics. 116(13):133521-1-133521-9. https://doi.org/10.1063/1.4897241S133521-1133521-911613Papamantellos, P. (1968). Verfeinerung der Tl2O3-Struktur mittels Neutronenbeugung. Zeitschrift für Kristallographie, 126(1-3), 143-146. doi:10.1524/zkri.1968.126.1-3.143Otto, H. H., Baltrusch, R., & Brandt, H.-J. (1993). Further evidence for Tl3+ in Tl-based superconductors from improved bond strength parameters involving new structural data of cubic Tl2O3. Physica C: Superconductivity, 215(1-2), 205-208. doi:10.1016/0921-4534(93)90382-zBerastegui, P., Eriksson, S., Hull, S., Garcı́a Garcı́a, F. ., & Eriksen, J. (2004). Synthesis and crystal structure of the alkaline-earth thallates MnTl2O3+n (M=Ca,Sr). Solid State Sciences, 6(5), 433-441. doi:10.1016/j.solidstatesciences.2004.03.003Prewitt, C. T., Shannon, R. D., Rogers, D. B., & Sleight, A. W. (1969). C rare earth oxide-corundum transition and crystal chemistry of oxides having the corundum structure. Inorganic Chemistry, 8(9), 1985-1993. doi:10.1021/ic50079a033Patra, C. R., & Gedanken, A. (2004). Rapid synthesis of nanoparticles of hexagonal type In2O3 and spherical type Tl2O3 by microwave irradiation. New Journal of Chemistry, 28(8), 1060. doi:10.1039/b400206gSwitzer, J. A. (1986). The n-Silicon/Thallium(III) Oxide Heterojunction Photoelectrochemical Solar Cell. Journal of The Electrochemical Society, 133(4), 722. doi:10.1149/1.2108662Phillips, R. J., Shane, M. J., & Switzer, J. A. (1989). Electrochemical and photoelectrochemical deposition of thallium(III) oxide thin films. Journal of Materials Research, 4(4), 923-929. doi:10.1557/jmr.1989.0923Van Leeuwen, R. A., Hung, C.-J., Kammler, D. R., & Switzer, J. A. (1995). Optical and Electronic Transport Properties of Electrodeposited Thallium(III) Oxide Films. The Journal of Physical Chemistry, 99(41), 15247-15252. doi:10.1021/j100041a047Bhattacharya, R. N. (2010). Thallium-Oxide Superconductors. High Temperature Superconductors, 129-151. doi:10.1002/9783527631049.ch6Weaver, C. D., Harden, D., Dworetzky, S. I., Robertson, B., & Knox, R. J. (2004). A Thallium-Sensitive, Fluorescence-Based Assay for Detecting and Characterizing Potassium Channel Modulators in Mammalian Cells. Journal of Biomolecular Screening, 9(8), 671-677. doi:10.1177/1087057104268749Geserich, H. P. (1968). Optische und elektrische Messungen an dünnen Thallium(III)-Oxydschichten. Physica Status Solidi (b), 25(2), 741-751. doi:10.1002/pssb.19680250227Goto, A., Yasuoka, H., Hayashi, A., & Ueda, Y. (1992). NMR Study of Metallic Thallic Oxides; Tl2O3-δ. Journal of the Physical Society of Japan, 61(4), 1178-1181. doi:10.1143/jpsj.61.1178Glans, P.-A., Learmonth, T., Smith, K. E., Guo, J., Walsh, A., Watson, G. W., … Egdell, R. G. (2005). Experimental and theoretical study of the electronic structure of HgO andTl2O3. Physical Review B, 71(23). doi:10.1103/physrevb.71.235109Kehoe, A. B., Scanlon, D. O., & Watson, G. W. (2011). Nature of the band gap ofTl2O3. Physical Review B, 83(23). doi:10.1103/physrevb.83.233202SHUKLA, V. N., & WIRTZ, G. P. (1977). Electrical Conduction in Single-Crystal Thallic Oxide: I, Crystals «As-Grown» from the Vapor in Air. Journal of the American Ceramic Society, 60(5-6), 253-258. doi:10.1111/j.1151-2916.1977.tb14119.xSHUKLA, V. N., & WIRTZ, G. P. (1977). Electrical Conduction in Single-Crystal Thallic Oxide: II, Effects of Annealing at 923oK in Oxygen Pressures from 0.01 to 1 Atmosphere. Journal of the American Ceramic Society, 60(5-6), 259-261. doi:10.1111/j.1151-2916.1977.tb14120.xWIRTZ, G. P., YU, C. J., & DOSER, R. W. (1981). Defect Chemistry and Electrical Properties of Thallium Oxide Single Crystals. Journal of the American Ceramic Society, 64(5), 269-275. doi:10.1111/j.1151-2916.1981.tb09600.xYokoo, M., Kawai, N., Nakamura, K. G., Kondo, K., Tange, Y., & Tsuchiya, T. (2009). Ultrahigh-pressure scales for gold and platinum at pressures up to 550 GPa. Physical Review B, 80(10). doi:10.1103/physrevb.80.104114Hammersley, A. P., Svensson, S. O., Hanfland, M., Fitch, A. N., & Hausermann, D. (1996). Two-dimensional detector software: From real detector to idealised image or two-theta scan. High Pressure Research, 14(4-6), 235-248. doi:10.1080/08957959608201408Holland, T. J. B., & Redfern, S. A. T. (1997). Unit cell refinement from powder diffraction data: the use of regression diagnostics. Mineralogical Magazine, 61(404), 65-77. doi:10.1180/minmag.1997.061.404.07Kraus, W., & Nolze, G. (1996). POWDER CELL – a program for the representation and manipulation of crystal structures and calculation of the resulting X-ray powder patterns. Journal of Applied Crystallography, 29(3), 301-303. doi:10.1107/s0021889895014920A. C. Larson and R. B. von Dreele , LANL Report No. 86–748, 2004.Toby, B. H. (2001). EXPGUI, a graphical user interface forGSAS. Journal of Applied Crystallography, 34(2), 210-213. doi:10.1107/s0021889801002242Hohenberg, P., & Kohn, W. (1964). Inhomogeneous Electron Gas. Physical Review, 136(3B), B864-B871. doi:10.1103/physrev.136.b864Kresse, G., & Furthmüller, J. (1996). Efficient iterative schemes forab initiototal-energy calculations using a plane-wave basis set. Physical Review B, 54(16), 11169-11186. doi:10.1103/physrevb.54.11169Kresse, G., & Joubert, D. (1999). From ultrasoft pseudopotentials to the projector augmented-wave method. Physical Review B, 59(3), 1758-1775. doi:10.1103/physrevb.59.1758Perdew, J. P., Ruzsinszky, A., Csonka, G. I., Vydrov, O. A., Scuseria, G. E., Constantin, L. A., … Burke, K. (2008). Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces. Physical Review Letters, 100(13). doi:10.1103/physrevlett.100.136406Mujica, A., Rubio, A., Muñoz, A., & Needs, R. J. (2003). High-pressure phases of group-IV, III–V, and II–VI compounds. Reviews of Modern Physics, 75(3), 863-912. doi:10.1103/revmodphys.75.863Chetty, N., Muoz, A., & Martin, R. M. (1989). First-principles calculation of the elastic constants of AlAs. Physical Review B, 40(17), 11934-11936. doi:10.1103/physrevb.40.11934Baroni, S., de Gironcoli, S., Dal Corso, A., & Giannozzi, P. (2001). Phonons and related crystal properties from density-functional perturbation theory. Reviews of Modern Physics, 73(2), 515-562. doi:10.1103/revmodphys.73.515Le Page, Y., & Saxe, P. (2002). Symmetry-general least-squares extraction of elastic data for strained materials fromab initiocalculations of stress. Physical Review B, 65(10). doi:10.1103/physrevb.65.104104Beckstein, O., Klepeis, J. E., Hart, G. L. W., & Pankratov, O. (2001). First-principles elastic constants and electronic structure ofα−Pt2Siand PtSi. Physical Review B, 63(13). doi:10.1103/physrevb.63.134112Gomis, O., Sans, J. A., Lacomba-Perales, R., Errandonea, D., Meng, Y., Chervin, J. C., & Polian, A. (2012). Complex high-pressure polymorphism of barium tungstate. Physical Review B, 86(5). doi:10.1103/physrevb.86.054121He, D., & Duffy, T. S. (2006). X-ray diffraction study of the static strength of tungsten to69GPa. Physical Review B, 73(13). doi:10.1103/physrevb.73.134106Errandonea, D., Boehler, R., Japel, S., Mezouar, M., & Benedetti, L. R. (2006). Structural transformation of compressed solid Ar: An x-ray diffraction study to114GPa. Physical Review B, 73(9). doi:10.1103/physrevb.73.092106Klotz, S., Chervin, J.-C., Munsch, P., & Le Marchand, G. (2009). Hydrostatic limits of 11 pressure transmitting media. Journal of Physics D: Applied Physics, 42(7), 075413. doi:10.1088/0022-3727/42/7/075413Birch, F. (1978). Finite strain isotherm and velocities for single-crystal and polycrystalline NaCl at high pressures and 300°K. Journal of Geophysical Research, 83(B3), 1257. doi:10.1029/jb083ib03p01257Angel, R. J. (2000). Equations of State. Reviews in Mineralogy and Geochemistry, 41(1), 35-59. doi:10.2138/rmg.2000.41.2Liu, D., Lei, W. W., Zou, B., Yu, S. D., Hao, J., Wang, K., … Zou, G. T. (2008). High-pressure x-ray diffraction and Raman spectra study of indium oxide. Journal of Applied Physics, 104(8), 083506. doi:10.1063/1.2999369Qi, J., Liu, J. F., He, Y., Chen, W., & Wang, C. (2011). Compression behavior and phase transition of cubic In2O3 nanocrystals. Journal of Applied Physics, 109(6), 063520. doi:10.1063/1.3561363García-Domene, B., Sans, J. A., Gomis, O., Manjón, F. J., Ortiz, H. M., Errandonea, D., … Segura, A. (2014). Pbca-Type In2O3: The High-Pressure Post-Corundum phase at Room Temperature. The Journal of Physical Chemistry C, 118(35), 20545-20552. doi:10.1021/jp5061599Angel, R. ., Mosenfelder, J. ., & Shaw, C. S. . (2001). Anomalous compression and equation of state of coesite. Physics of the Earth and Planetary Interiors, 124(1-2), 71-79. doi:10.1016/s0031-9201(01)00184-4Pereira, A. L. J., Gracia, L., Santamaría-Pérez, D., Vilaplana, R., Manjón, F. J., Errandonea, D., … Beltrán, A. (2012). Structural and vibrational study of cubic Sb2O3under high pressure. Physical Review B, 85(17). doi:10.1103/physrevb.85.174108Pereira, A. L. J., Errandonea, D., Beltrán, A., Gracia, L., Gomis, O., Sans, J. A., … Popescu, C. (2013). Structural study of α-Bi2O3under pressure. Journal of Physics: Condensed Matter, 25(47), 475402. doi:10.1088/0953-8984/25/47/475402Choudhury, N., & Chaplot, S. L. (2006). Ab initiostudies of phonon softening and high-pressure phase transitions ofα-quartzSiO2. Physical Review B, 73(9). doi:10.1103/physrevb.73.094304Yusa, H., Tsuchiya, T., Sata, N., & Ohishi, Y. (2008). Rh2O3(II)-type structures inGa2O3andIn2O3under high pressure: Experiment and theory. Physical Review B, 77(6). doi:10.1103/physrevb.77.064107Yusa, H., Tsuchiya, T., Tsuchiya, J., Sata, N., & Ohishi, Y. (2008). α-Gd2S3-type structure inIn2O3: Experiments and theoretical confirmation of a high-pressure polymorph in sesquioxide. Physical Review B, 78(9). doi:10.1103/physrevb.78.092107Gurlo, A., Dzivenko, D., Kroll, P., & Riedel, R. (2008). High-pressure high-temperature synthesis of Rh2O3-II-type In2O3polymorph. physica status solidi (RRL) - Rapid Research Letters, 2(6), 269-271. doi:10.1002/pssr.200802201Bekheet, M. F., Schwarz, M. R., Lauterbach, S., Kleebe, H.-J., Kroll, P., Stewart, A., … Gurlo, A. (2013). In situhigh pressure high temperature experiments in multi-anvil assemblies with bixbyite-type In2O3and synthesis of corundum-type and orthorhombic In2O3polymorphs. High Pressure Research, 33(3), 697-711. doi:10.1080/08957959.2013.834896Bekheet, M. F., Schwarz, M. R., Lauterbach, S., Kleebe, H.-J., Kroll, P., Riedel, R., & Gurlo, A. (2013). Orthorhombic In2O3: A Metastable Polymorph of Indium Sesquioxide. Angewandte Chemie International Edition, 52(25), 6531-6535. doi:10.1002/anie.201300644Biesterbos, J. W. M., & Hornstra, J. (1973). The crystal structure of the high-temperature, low-pressure form of Rh2O3. Journal of the Less Common Metals, 30(1), 121-125. doi:10.1016/0022-5088(73)90013-1Wang, L., Pan, Y., Ding, Y., Yang, W., Mao, W. L., Sinogeikin, S. V., … Mao, H. (2009). High-pressure induced phase transitions of Y2O3 and Y2O3:Eu3+. Applied Physics Letters, 94(6), 061921. doi:10.1063/1.3082082Husson, E., Proust, C., Gillet, P., & Itié, J. . (1999). Phase transitions in yttrium oxide at high pressure studied by Raman spectroscopy. Materials Research Bulletin, 34(12-13), 2085-2092. doi:10.1016/s0025-5408(99)00205-6Meyer, C., Sanchez, J. P., Thomasson, J., & Itié, J. P. (1995). Mössbauer and energy-dispersive x-ray-diffraction studies of the pressure-induced crystallographic phase transition inC-typeYb2O3. Physical Review B, 51(18), 12187-12193. doi:10.1103/physrevb.51.12187Guo, Q., Zhao, Y., Jiang, C., Mao, W. L., Wang, Z., Zhang, J., & Wang, Y. (2007). Pressure-Induced Cubic to Monoclinic Phase Transformation in Erbium Sesquioxide Er2O3. Inorganic Chemistry, 46(15), 6164-6169. doi:10.1021/ic070154gGuo, Q., Zhao, Y., Jiang, C., Mao, W. L., & Wang, Z. (2008). Phase transformation in Sm2O3 at high pressure: In situ synchrotron X-ray diffraction study and ab initio DFT calculation. Solid State Communications, 145(5-6), 250-254. doi:10.1016/j.ssc.2007.11.019Nishio-Hamane, D., Katagiri, M., Niwa, K., Sano-Furukawa, A., Okada, T., & Yagi, T. (2009). A new high-pressure polymorph of Ti2O3: implication for high-pressure phase transition in sesquioxides. High Pressure Research, 29(3), 379-388. doi:10.1080/08957950802665747Ovsyannikov, S. V., Wu, X., Shchennikov, V. V., Karkin, A. E., Dubrovinskaia, N., Garbarino, G., & Dubrovinsky, L. (2010). Structural stability of a golden semiconducting orthorhombic polymorph of Ti2O3under high pressures and high temperatures. Journal of Physics: Condensed Matter, 22(37), 375402. doi:10.1088/0953-8984/22/37/375402Ono, S., Funakoshi, K., Ohishi, Y., & Takahashi, E. (2005). In situx-ray observation of the phase transformation of Fe2O3. Journal of Physics: Condensed Matter, 17(2), 269-276. doi:10.1088/0953-8984/17/2/003Santillán, J., Shim, S.-H., Shen, G., & Prakapenka, V. B. (2006). High-pressure phase transition in Mn2O3: Application for the crystal structure and preferred orientation of the CaIrO3type. Geophysical Research Letters, 33(15). doi:10.1029/2006gl026423Yao, H., Ouyang, L., & Ching, W.-Y. (2007). Ab Initio Calculation of Elastic Constants of Ceramic Crystals. Journal of the American Ceramic Society, 90(10), 3194-3204. doi:10.1111/j.1551-2916.2007.01931.xBorn, M. (1940). On the stability of crystal lattices. I. Mathematical Proceedings of the Cambridge Philosophical Society, 36(2), 160-172. doi:10.1017/s0305004100017138Wallace, D. C. (1970). Thermoelastic Theory of Stressed Crystals and Higher-Order Elastic Constants. Solid State Physics, 301-404. doi:10.1016/s0081-1947(08)60010-7Wang, J., Yip, S., Phillpot, S. R., & Wolf, D. (1993). Crystal instabilities at finite strain. Physical Review Letters, 71(25), 4182-4185. doi:10.1103/physrevlett.71.4182Wang, J., Li, J., Yip, S., Phillpot, S., & Wolf, D. (1995). Mechanical instabilities of homogeneous crystals. Physical Review B, 52(17), 12627-12635. doi:10.1103/physrevb.52.12627Karki, B. B., Stixrude, L., & Wentzcovitch, R. M. (2001). High-pressure elastic properties of major materials of Earth’s mantle from first principles. Reviews of Geophysics, 39(4), 507-534. doi:10.1029/2000rg000088Krasilnikov, O. M., Belov, M. P., Lugovskoy, A. V., Mosyagin, I. Y., & Vekilov, Y. K. (2014). Elastic properties, lattice dynamics and structural transitions in molybdenum at high pressures. Computational Materials Science, 81, 313-318. doi:10.1016/j.commatsci.2013.08.038Reuss, A. (1929). Berechnung der Fließgrenze von Mischkristallen auf Grund der Plastizitätsbedingung für Einkristalle . ZAMM - Zeitschrift für Angewandte Mathematik und Mechanik, 9(1), 49-58. doi:10.1002/zamm.19290090104Hill, R. (1952). The Elastic Behaviour of a Crystalline Aggregate. Proceedings of the Physical Society. Section A, 65(5), 349-354. doi:10.1088/0370-1298/65/5/307Wu, Z., Zhao, E., Xiang, H., Hao, X., Liu, X., & Meng, J. (2007). Crystal structures and elastic properties of superhardIrN2andIrN3from first principles. Physical Review B, 76(5). doi:10.1103/physrevb.76.054115Caracas, R., & Boffa Ballaran, T. (2010). Elasticity of (K,Na)AlSi3O8 hollandite from lattice dynamics calculations. Physics of the Earth and Planetary Interiors, 181(1-2), 21-26. doi:10.1016/j.pepi.2010.04.004Liu, Q.-J., Liu, Z.-T., & Feng, L.-P. (2011). First-Principles Calculations of Structural, Elastic and Electronic Properties of Tetragonal HfO2under Pressure. Communications in Theoretical Physics, 56(4), 779-784. doi:10.1088/0253-6102/56/4/31Pugh, S. F. (1954). XCII. Relations between the elastic moduli and the plastic properties of polycrystalline pure metals. The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, 45(367), 823-843. doi:10.1080/14786440808520496Grimvall, G., Magyari-Köpe, B., Ozoliņš, V., & Persson, K. A. (2012). Lattice instabilities in metallic elements. Reviews of Modern Physics, 84(2), 945-986. doi:10.1103/revmodphys.84.945Sharma, S. M., & Sikka, S. K. (1996). Pressure induced amorphization of materials. Progress in Materials Science, 40(1), 1-77. doi:10.1016/0079-6425(95)00006-2Richet, P., & Gillet, P. (1997). Pressure-induced amorphization of minerals: a review. European Journal of Mineralogy, 9(5), 907-934. doi:10.1127/ejm/9/5/090

Manejo de la inmunosupresión en pacientes trasplantados de riñón con COVID19. Estudio multicéntrico nacional derivado del registro COVID de la Sociedad Española de Nefrología

Introduction: SARS CoV2 infection has had a major impact on renal transplant patients with a high mortality in the first months of the pandemic. Intentional reduction of immunosuppressive therapy has been postulated as one of the cornerstone in the management of the infection in the absence of targeted antiviral treatment. This has been modified according to the patient`s clinical situation and its effect on renal function or anti-HLA antibodies in the medium term has not been evaluated.Objectives: Evaluate the management of immunosuppressive therapy made during SARS-CoV2 infection, as well as renal function and anti-HLA antibodies in kidney transplant patients 6 months after COVID19 diagnosis.Material and methods: Retrospective, national multicentre, retrospective study (30 centres) of kidney transplant recipients with COVID19 from 01/02/20 to 31/12/20. Clinical variables were collected from medical records and included in an anonymised database. SPSS statistical software was used for data analysis.Results: renal transplant recipients with COVID19 were included (62.6% male), with a mean age of 57.5 years. The predominant immunosuppressive treatment prior to COVID19 was triple therapy with prednisone, tacrolimus and mycophenolic acid (54.6%) followed by m-TOR inhibitor regimens (18.6%). After diagnosis of infection, mycophenolic acid was discontinued in 73.8% of patients, m-TOR inhibitor in 41.4%, tacrolimus in 10.5% and cyclosporin A in 10%. In turn, 26.9% received dexamethasone and 50.9% were started on or had their baseline prednisone dose increased. Mean creatinine before diagnosis of COVID19, at diagnosis and at 6 months was: 1.7 +/- 0.8, 2.1 +/- 1.2 and 1.8 +/- 1 mg/dl respectively (p < 0.001). 56.9% of the patients (N = 350) were monitored for anti-HLA antibodies. 94% (N = 329) had no anti-HLA changes, while 6% (N = 21) had positive anti-HLA antibodies. Among the patients with donor-specific antibodies post-COVID19 (N = 9), 7 patients (3.1%) had one immunosuppressant discontinued (5 patients had mycophenolic acid and 2 had tacrolimus), 1 patient had both immunosuppressants discontinued (3.4%) and 1 patient had no change in immunosuppression (1.1%), these differences were not significant.Conclusions: The management of immunosuppressive therapy after diagnosis of COVID19 was primarily based on discontinuation of mycophenolic acid with very discrete reductions or discontinuations of calcineurin inhibitors. This immunosuppression management did not influence renal function or changes in anti-HLA antibodies 6 months after diagnosis