Computational Chemistry Meets Experiments for Explaining the Geometry, Electronic Structure, and Optical Properties of Ca10V6O25

Author(s)

Teixeira, Mayara Mondego ^[1] ; de Oliveira, Regiane Cristina ^[1] ; Carvalho Oliveira, Marisa ^{[2, 1]} ; Pontes Ribeiro, Renan Augusto ^[3] ; de Lazaro, Sergio R. ^[3] ; Li, Maximo Siu ^[4] ; Chiquito, Adenilson J. ^[5] ; Gracia, Lourdes ^[6] ; Andres, Juan ^[2] ; Longo, Elson ^[1]

Affiliation

^[1] Univ Fed Sao Carlos, CDMF UFSCar, POB 676, BR-13565905 Sao Carlos, SP - Brazil

^[2] Univ Jaume 1, Dept Quim Fis & Analit, Castellon de La Plana 12071 - Spain

^[3] Univ Estadual Ponta GrosCsa, Dept Quim, Ave Gen Carlos Cavalcanti 4748, BR-84030900 Ponta Grossa, PR - Brazil

^[4] Univ Sao Paulo, IFSC, POB 369, BR-13560970 Sao Paulo - Brazil

^[5] Univ Fed Sao Carlos, Dept Fis, Rod Washington Luiz, Km 235, CP 676, BR-13565905 Sao Carlos, SP - Brazil

^[6] Univ Valencia, Dept Quim Fis, E-46100 Burjassot - Spain

• Document type: Journal article
• Source: Inorganic Chemistry; v. 57, n. 24, p. 15489-15499, DEC 17 2018.
• Web of Science Citations: 0

Abstract

In this paper, we present a combined experimental and theoretical study to disclose, for the first time, the structural, electronic, and optical properties of Ca10V6O25 crystals. The microwave -assisted hydrothermal (MAH) method has been employed to synthesize these crystals with different morphologies, within a short reaction time at 120 degrees C. First-principle quantum mechanical calculations have been performed at the density functional theory level to obtain the geometry and electronic properties of Ca10V6O25 crystal in the fundamental and excited electronic states (singlet and triplet). These results, combined with the measurements of X-ray diffraction (XRD) and Rietveld refinements, confirm that the building blocks lattice of the Ca10V6O25 crystals consist of three types of distorted 6-fold coordination {[}CaO6] clusters: octahedral, prism and pentagonal pyramidal, and distorted tetrahedral {[}VO4] clusters. Theoretical and experimental results on the structure and vibrational frequencies are in agreement. Thus, it was possible to assign the Raman modes for the Ca10V6O25 superstructure, which will allow us to show the structure of the unit cell of the material, as well as the coordination of the Ca and V atoms. This also allowed us to understand the charge transfer process that happens in the singlet state (s) and the excited states, singlet (s{*}) and triplet (t{*}), generating the photoluminescence emissions of the Ca10V6O25 crystals. (AU)

• FAPESP's process: 13/26671-9 - Theoretical and experimental study of multifunctional semiconductors
• Grantee: Amanda Fernandes Gouveia
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 13/07296-2 - CDMF - Center for the Development of Functional Materials
• Grantee: Elson Longo da Silva
• Support Opportunities: Research Grants - Research, Innovation and Dissemination Centers - RIDC