Topic
Valence (chemistry)
About: Valence (chemistry) is a research topic. Over the lifetime, 24937 publications have been published within this topic receiving 645252 citations. The topic is also known as: valency.
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154 citations
TL;DR: The application of RIXS as a probe of frontier molecular orbitals in a heme enzyme demonstrates the potential of this method for the study of metal sites in highly covalent coordination sites in bioinorganic chemistry.
153 citations
TL;DR: Ab initio ligand field theory (AILFT) as discussed by the authors allows one to unambiguously extract all ligand fields parameters from relatively straightforward multi-reference ab initio calculations, and applies to mononuclear complexes in d n or f n configurations.
153 citations
TL;DR: In this paper, the authors describe In+ species using photoluminescence (PL) and X-ray absorption fine structure (XAFS) analysis, and demonstrate that In+ exists in a metastable amorphous network, which is the origin of the observed luminescent properties.
Abstract: Valence control of polyvalent cations is important for functionalization of various kinds of materials. Indium oxides have been used in various applications, such as indium tin oxide in transparent electrical conduction films. However, although metastable In+ (5 s2 configuration) species exhibit photoluminescence (PL), they have attracted little attention. Valence control of In+ cations in these materials will be important for further functionalization. Here, we describe In+ species using PL and X-ray absorption fine structure (XAFS) analysis. Three absorption bands in the UV region are attributed to the In+ centre: two weak forbidden bands (1S0 → 3P1, 1S0 → 3P2) and a strong allowed band (1S0 → 1P1). The strongest PL excitation band cannot be attributed to the conventional allowed transition to the singlet excited state. Emission decay of the order of microseconds suggests that radiative relaxation occurs from the triplet excitation state. The XAFS analysis suggests that these In+ species have shorter In–O distances with lower coordination numbers than in In2O3. These results clearly demonstrate that In+ exists in a metastable amorphous network, which is the origin of the observed luminescent properties.
153 citations
TL;DR: The analysis elucidats that the band structures are mainly governed by the orbits of phosphorus, oxygen and europium, and the sharp peaks of theEuropium f-orbit occur at the top of the valence bands.
Abstract: In this study, the Ba3Eu(PO4)3 and Sr3Eu(PO4)3 compounds were synthesized and the crystal structures were determined for the first time by Rietveld refinement using powder X-ray diffraction (XRD) patterns. Ba3Eu(PO4)3 crystallizes in cubic space group I3d, with cell parameters of a = 10.47996(9) A, V = 1151.01(3) A3 and Z = 4; Ba2+ and Eu3+ occupy the same site with partial occupancies of 3/4 and 1/4, respectively. Besides, in this structure, there exists two distorted kinds of the PO4 polyhedra orientation. Sr3Eu(PO4)3 is isostructural to Ba3Eu(PO4)3 and has much smaller cell parameters of a = 10.1203(2) A, V = 1036.52(5) A3. The bandgaps of Ba3Eu(PO4)3 and Sr3Eu(PO4)3 are determined to be 4.091 eV and 3.987 eV, respectively, based on the UV–Vis diffuse reflectance spectra. The photoluminescence measurements reveal that, upon 396 nm n-UV light excitation, Ba3Eu(PO4)3 and Sr3Eu(PO4)3 exhibit orange-red emission with two main peaks at 596 nm and prevailing 613 nm, corresponding to the 5D0 → 7F1 and 5D0 → 7F2 transitions of Eu3+, respectively. The dynamic disordering in the crystal structures contributes to the broadening of the luminescence spectra. The electronic structure of the phosphates was calculated by the first-principles method. The analysis elucidats that the band structures are mainly governed by the orbits of phosphorus, oxygen and europium, and the sharp peaks of the europium f-orbit occur at the top of the valence bands.
153 citations