A combined theoretical and experimental study of electronic structure and optical properties of β-ZnMoO4 microcrystals

In this paper, a combined theoretical and experimental study on the electronic structure and photoluminescence (PL) properties of beta zinc molybdate ( -ZnMoO4) microcrystals synthesized by the hydrothermal method has been employed. These crystals were structurally characterized by means of X-ray diffraction (XRD), Rietveld refinement, Fourier transform Raman (FT-Raman) and Fourier transform infrared (FT-IR) spectroscopies. Their optical properties were investigated by ultraviolet-visible (UV-vis) absorption spectroscopy and PL measurements. First-principles quantum mechanical calculations based on the density functional theory at the B3LYP calculation level have been carried out. XRD patterns, Rietveld refinement, FT-Raman and FT-IR spectra showed that these crystals have a wolframite-type monoclinic structure. The Raman and IR frequencies experimental results are in reasonable agreement with theoretically calculated results. UV-vis absorption measurements shows an optical band gap value of 3.17 eV, while the calculated band structure has a value of 3.22 eV. The density of states indicate that the main orbitals involved in the electronic structure of -ZnMoO4 crystals are (O2p-valence band and Mo 4d-conduction band). Finally, PL properties of -ZnMoO4 crystals are explained by distortions effects in octahedral [ZnO6] and [MoO6] clusters and inhomogeneous electronic distribution into the lattice with the electron density map

Toward an Understanding of the Growth of Ag Filaments on α-Ag2WO4 and Their Photoluminescent Properties: A Combined Experimental and Theoretical Study

A combined experimental and theoretical study was conducted on the structure and electronic properties of α-Ag2WO4 to clarify the nucleation and growth processes of Ag filaments on α-Ag2WO4 crystals induced by electron beam irradiation under electron microscopy. X-ray diffraction with Rietveld analysis, micro-Raman and Fourier-transform infrared spectroscopy were used to analyze the structural order/disorder of α-Ag2WO4 crystals. These complementary techniques indicated that the microwave-assisted hydrothermal method employed in the synthesis of α-Ag2WO4 crystals leads to the freezing of distorted [WO6] and [AgOy] (y = 2, 4, 6 and 7) clusters as the constituent polyhedra of α-Ag2WO4. On the basis of the theoretical and experimental results, we provide a complete assignment of the structure of α-Ag2WO4 and describe the relationship among the disorder, nucleation growth, rate of Ag formation, and photoluminescence behavior before and after the irradiation of the accelerated electron beam. Density functional theory (DFT) studies indicated significant changes in the order–disorder of the initial α-Ag2WO4electronic structure, with a decrease in the band gap value from 3.55 to 2.72 eV. The first stages of the electron irradiation on α-Ag2WO4 crystal were investigated by DFT calculations, and we have derived a mechanism to describe the formation and growth of Ag filaments during the electronic excitation of the [AgO2] cluster.This work is financially supported by the National Council for Scientific and Technological Development (CNPq), São Paulo Research Foundation (FAPESP), Prometeo/2009/053 (Generalitat Valenciana) and Ministerio de Economía y Competitividad (Spain), CTQ2012-36253-C03-02, and the Spanish–Brazilian program (PHB2009-0065-PC) for their financial support. TEM facilities were provided by LME-IQ-UNESP

Vascular Flora Of The Legado Das Águas, Reserva Votorantim, Municipalities Of Tapiraí, Miracatú And Juquiá, São Paulo, Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)We present a list of vascular plants found in Legado das Águas, Reserva Votorantim, a private reserve having an area of approximately 35,000 ha that spans the municipalities of Tapiraí, Miracatú, and Juquiá, in the state of São Paulo, Brazil. The reserve is part of a complex of state-protected areas including Alto Ribeira Touristic State Park, Intervales State Park, Carlos Botelho State Park, Jurupará State Park, and Serra do Mar State Park. Together, these form an important and large area of continuous and well-preserved forest. Our study, which involved two main floristic surveys in March/April 2013 and April 2014, recorded 768 species, representing 131 families and 432 genera. The majority of species were angiosperms (619) representing 106 families and 370 genera. There were also two species of gymnosperms belonging to two genera in separate families; 147 species of ferns and lycophytes belonging to 23 families and 60 genera. In demonstrating the presence of almost 800 species of plants, of which 16 are threatened, our study highlights the importance of floristic surveys and the critical role of private protected areas in managing and preserving native flora. © 2016 Check List and Authors.1262011/22923-8, FAPESP, Fundação de Amparo à Pesquisa do Estado de São Paulo2015/9444-4, FAPESP, Fundação de Amparo à Pesquisa do Estado de São PauloFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP