Pressure-Driven Symmetry-Preserving Phase Transitions in Co(IO3)2
| Autor: | Daniel Errandonea, Zoulikha Hebboul, Akun Liang, Robin Turnbull, Francisco Javier Manjón, Alfonso Muñoz, Ibraheem Yousef, Plácida Rodríguez-Hernández, Catalin Popescu, Enrico Bandiello |
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| Rok vydání: | 2021 |
| Předmět: |
Diffraction
Phase transition Electron pair Materials science chemistry.chemical_element Infrared spectroscopy Synchrotron Surfaces Coatings and Films Electronic Optical and Magnetic Materials law.invention symbols.namesake chemistry.chemical_compound General Energy chemistry law Chemical physics FISICA APLICADA symbols Physical and Theoretical Chemistry Raman spectroscopy Cobalt Iodate |
| Zdroj: | RiuNet. Repositorio Institucional de la Universitat Politécnica de Valéncia instname |
| ISSN: | 1932-7455 1932-7447 |
| DOI: | 10.1021/acs.jpcc.1c04659 |
| Popis: | [EN] High-pressure synchrotron X-ray diffraction studies of cobalt iodate, Co(IO3)(2), reveal a counterintuitive pressure-induced expansion along certain crystallographic directions. High-pressure Raman and infrared spectroscopy, combined with density-functional theory calculations, reveal that with increasing pressure, it becomes energetically favorable for certain I-O bonds to increase in length over the full range of pressure studied up to 28 GPa. This phenomenon is driven by the high-pressure behavior of iodate ion lone electron pairs. Two pressure-induced isosymmetric monoclinic-monoclinic phase transitions are observed at around 3.0 and 9.0 GPa, which are characterized by increasing oxygen coordination of the iodine atoms and the probable formation of pressure-induced metavalent bonds. Pressure-volume equations of state are presented, as well as a detailed discussion of the pressure dependences of the observed Raman- and infrared-active modes, which clarifies previous inconsistencies in the literature. This work was supported by the Generalitat Valenciana under Project PROMETEO 2018/123-EFIMAT and by the Spanish Ministerio de Ciencia, Universidades, e Investigacion under Projects PID2019-106383GB-41/42/43, as well as through MALTA Consolider Team research network (RED2018102612-T). A.M. and P.R.-H. acknowledge computing time provided by Red Espan~ola de Supercomputacion (RES) and the MALTA Consolider Team cluster. D.E. acknowledges the resources and technical assistance provided by the Informatics Service of Universitat de Valencia through the Tirant III cluster. A.L. and D.E. would like to thank the Generalitat Valenciana for the Ph.D. Fellowship no. GRISOLIAP/2019/025. R.T. acknowledges funding from the Spanish Ministerio de Economia y Competitividad (MINECO) via the Juan de la Cierva Formacion fellowship (FJC2018-036185-I). C.P. is thankful for the financial support of the Spanish Mineco Project no. FIS2017-83295-P. E.B would like to thank the University of Valencia for his "Attraccio de Talent" postdoctoral contract (UV-INV_POSTDOC19-1026935). The authors thank Sandrine Beauquis from Symme, Universite Savoie Mont Blanc (France), for her technical assistance concerning the SEM and ADX analyses. PXRD experiments were performed at the MSPD beamline of ALBA Synchrotron (experiment no. 2019083663). IR experiments were performed at the MIRAS beamline of ALBA Synchrotron (experiment no. 2020024118). |
| Databáze: | OpenAIRE |
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