A theoretical study of the Pnma and R3m phases of Sb2S3, Bi2S3, and Sb2Se3

[EN] We report a comparative theoretical study of the Pnma and R3m phases of Sb2S3, Bi2S3, and Sb2Se3 close to ambient pressure. Our enthalpy calculations at 0 K show that at ambient pressure the R3m (tetradymite-like) phase of Sb2Se3 is energetically more stable than the Pnma phase, contrary to what is observed for Sb2S3 and Bi2S3, and irrespective of the exchange-correlation functional employed in the calculations. The result for Sb2Se3 is in contradiction to experiments in which all three compounds are usually grown in the Pnma phase. This result is further confirmed by free-energy calculations taking into account the temperature dependence of unit-cell volumes and phonon frequencies. Lattice dynamics and elastic tensor calculations further show that both the Pnma and R3m phases of Sb2Se3 are dynamically and mechanically stable at zero applied pressure. Since these results suggest that the formation of the R3m phase of Sb2Se3 should be feasible under close to ambient conditions, we provide a theoretical crystal structure and simulated Raman and infrared spectra to help in its identification. We also discuss the results of the two published works that have claimed to have synthesized tetradymite-like Sb2Se3. Finally, the stability of the R3m phase across the three group-15 A(2)X(3) sesquichalcogenides is analysed based on their van der Waals gap and X-X in-plane geometry.This publication is part of the MALTA Consolider Team network (RED2018-102612-T) (MINECO/AEI/10.13039/501100003329), and is supported by I + D + i project PID2019-106383GB41/42/43 (MCIN/AEI/10.13039/501100011033), by the PROMETEO/2018/123(EFIMAT) and CIPROM/2021/075 (GREENMAT) projects (Generalitat Valenciana), and by the European Union Horizon 2020 research and innovation programme under a Marie Sklodowska-Curie grant agreement (785789-COMEX). E. L. d. S., A. M., and P. R.-H. acknowledge computing time provided on the MALTA-Cluster at the University of Oviedo and on the MareNostrum facility through Red Espanola de Supercomputacion (RES) with technical support provided by the Barcelona Supercomputing Center (QCM-2018-3-0032). E. L. d. S. also acknowledges the Network of Extreme Conditions Laboratories (NECL), financed by FCT and co-financed by NORTE 2020 through the Portugal 2020 and FEDER programmes. J. M. S. is grateful to UK Research and Innovation for the support of a Future Leaders Fellowship (MR/T043121/1) and to the University of Manchester for the previous support of a Presidential Fellowship.Da Silva, EL.; Skelton, JM.; Rodríguez-Hernández, P.; Muñoz, A.; Santos, MC.; Martínez-García, D.; Vilaplana Cerda, RI.... (2022). A theoretical study of the Pnma and R3m phases of Sb2S3, Bi2S3, and Sb2Se3. Journal of Materials Chemistry C. 10(40):15061-15074. https://doi.org/10.1039/d2tc01484j1506115074104

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. 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Experimental and Theoretical Study of SbPO4 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.9b02268.[EN] SbPO4 is a complex monoclinic layered material characterized by a strong activity of the nonbonding lone electron pair (LEP) of Sb. The strong cation LEP leads to the formation of layers piled up along the a axis and linked by weak SbO electrostatic interactions. In fact, Sb has 4-fold coordination with O similarly to what occurs with the P-O coordination, despite the large difference in ionic radii and electronegativity between both elements. Here we report a joint experimental and theoretical study of the structural and vibrational properties of SbPO4 at high pressure. We show that SbPO4 is not only one of the most compressible phosphates but also one of the most compressible compounds of the ABO(4) family. Moreover, it has a considerable anisotropic compression behavior, with the largest compression occurring along a direction close to the a axis and governed by the compression of the LEP and the weak interlayer Sb-O bonds. The strong compression along the a axis leads to a subtle modification of the monoclinic crystal structure above 3 GPa, leading from a 2D to a 3D material. Moreover, the onset of a reversible pressure-induced phase transition is observed above 9 GPa, which is completed above 20 GPa. We propose that the high-pressure phase is a triclinic distortion of the original monoclinic phase. The understanding of the compression mechanism of SbPO4 can aid to improve the ion intercalation and catalytic properties of this layered compound.The authors acknowledge financial support from the Brazilian Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq - 159754/2018-6, 307199/2018-5, 422250/20163, 201050/2012-9), FAPESP (2013/07793-6), Spanish Ministerio de Economia y Competitividad (MINECO) under projects MALTA Consolider Ingenio 2010 network (MAT2015-71070-REDC and RED2018-102612-T), MAT2016-75586-C4-1/2/3-P, PGC2018-097520-A-I00, FIS2017-83295-P, and PGC2018-094417-B-I00 from Generalitat Valenciana under project PROMETEO/2018/123, and the European Comission under project COMEX. D.S.-P., JA.S., and A.O.d.l.R. acknowledge "Ramim y Cajal" Fellowships for financial support (RyC-2014-15643, RYC-2015-17482, and RyC-2016-20301, respectively). E.L.d. 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Electronic properties of doped silicon nanocrystals

No presente trabalho estuda-se, através de modelação computacional baseada na teoria do funcional da densidade, os efeitos de impurezas em nanocristais de silício passivados com hidrogénio. São calculados os níveis de energia das impurezas intersticiais mais propícias à dopagem de tipo-n e p para os sistemas con nados, nomeadamente os três primeiros elementos pertencentes ao grupo dos alcalinos, Li, Na e K, e os três primeiros halogéneos, F, Cl e Br. Observou-se que à temperatura ambiente estas impurezas não contribuem com portadores de carga (electrões ou lacunas) para os estados HOMO nem LUMO. Este facto resulta do con namento da superfície e do meio dieléctrico fraco existente no nanocristal. Os níveis de energia para o P, B e o Duplo Dador Térmico do modelo da cadeia O5 foram também calculados por forma a comparar o comportamento destes nos sistemas con nados com o comportamento, bem estabelecido, na matéria extensa. Níveis de energia profundos no hiato também foram observados para estas impurezas

Solid State Chemistry: Computational Chemical Analysis for Materials Science

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