Search results for "Splitting"
showing 10 items of 220 documents
Mössbauer spectroscopy of mono-organotin(IV) derivatives
1974
Abstract The Mossbauer parameters isomer shift, δ, and quadrupole splitting, ΔE, of mono-organotin compounds insofar investigated have been collected and tabulated. It is demonstrated that isomer shifts consistently depend on ligand electronegativities and coordination numbers, from which it is deduced that RSn IV behave much more as Sn IV rather than R 2 Sn IV and R 3 Sn IV derivatives. The changes of δ for RSn IV are then interpreted by hypotheses analogous to those advanced for Sn IV and its adducts and complexes. It is also inferred that in RSn IV compounds there is a consistent s-character in all tin-ligand atom bonds.
The hydrolysis of Me2SnIV and Me3SnIV moieties monitored through 119Sn Mössbauer spectroscopy
1991
Abstract The 119 Sn Mossbauer parameters δ, isomer shift, and Δ E , nuclear quadrupole splitting, have been determined in frozen aqueous solutions of Me 2 Sn IV and Me 3 Sn IV moieties at varying pH. The resulting functions n versus pH (where n is the average number of protons released per mole of the organotin aquocation) agree satisfactorily with functions from potentiometry. The structures of the aquocations, as well as of the hydroxides, and of the mono-hydroxo complex [Me 2 Sn(OH)(OH 2 ) n ] + , are correlated to the Δ E exp data by point-charge model calculations.
Field-induced single molecule magnet behavior of a dinuclear cobalt(II) complex: a combined experimental and theoretical study.
2020
Two dinuclear cobalt(ii) complexes, [(dmso)CoIIL1(μ-(m-NO2)C6H4COO)CoII(NCS)] (1) and [(dmso)CoIIL2(μ-(m-NO2)C6H4COO)CoII(NCS)] (2) [dmso = dimethylsulfoxide, H2L1 = (2,2-dimethyl-1,3-propanediyl)bis(iminomethylene)bis(6-methoxyphenol) and H2L2 = (2,2-dimethyl-1,3-propanediyl)bis(iminomethylene)bis(6-ethoxyphenol)] have been synthesized and structurally characterized by single-crystal X-ray diffraction, magnetic-susceptibility measurements and various spectroscopic techniques. Each complex contains a cobalt(ii) center with a slightly distorted octahedral geometry and a second cobalt(ii) center with a distorted trigonal prismatic one. To obtain insight into the physical nature of weak non-co…
2D and 3D Anilato-Based Heterometallic M(I)M(III) Lattices: The Missing Link
2015
The similar bis-bidentate coordination mode of oxalato and anilato-based ligands is exploited here to create the first examples of 2D and 3D heterometallic lattices based on anilato ligands combining M(I) and a M(III) ions, phases already observed with oxalato but unknown with anilato-type ligands. These lattices are prepared with alkaline metal ions and magnetic chiral tris(anilato)metalate molecular building blocks: [M(III)(C6O4X2)3](3-) (M(III) = Fe and Cr; X = Cl and Br; (C6O4X2)(2-) = dianion of the 3,6-disubstituted derivatives of 2,5-dihydroxy-1,4-benzoquinone, H4C6O4). The new compounds include two very similar 2D lattices formulated as (PBu3Me)2[NaCr(C6O4Br2)3] (1) and (PPh3Et)2[KF…
Mössbauer effect study of the electronic ground state of iron(II) in [57FexM1−x(bipy)3](ClO4)2 (M = Mn, Ni, Zn) and [57FexM1−x(phen)3](ClO4)2 (M = Ni…
1980
Earlier work in our laboratory on the effect of metal dilution on the 5T2(Oh ⇌ 1A1(Oh) equilibrium in polycrystalline spin crossover systems of iron(II) has shown that the relative stability of the high spin state, 5T2(Oh), at a given temperature, increases markedly with decreasing iron concentration. These results have initiated the present work. Using 57Fe Mossbauer spectroscopy, we have investigated the electronic ground state of iron(II) in the highly diluted solid solutions [FexM1−xL3] with L = bipy, M = Mn, Ni, Zn, x ≲ 0.005 and L = phen, M = Ni, Zn, x ≲ 0.005. Although the critical field potential (Vc) of the pure iron complexes, which are known to be low spin, is reported to be not …
EXTENDED HÜCKEL MOLECULAR ORBITAL CALCULATION OF THE TEMPERATURE DEPENDENCE OF THE QUADRUPOLE SPLITTING OF [Fe(H2O)6] SiF6 AND KFeCl3
1976
A number of papers have appeared in which the temperature dependence of the quadrupole splitting has been treated, whereby covalency effects have been considered by introducing the orbital reduction factor k, with k ranging from 1.-0.7. There are, however, two problems : (1) k is unisotropic if the symmetry is lower than cubic, (2) the spin orbit coupling of the ligand electrons are usually neglected. These two problems have been treated here by using SCCEHMO [1] calculations on two examples, [Fe(H2O)6]SiF6 and KFeCl3, which have been previously delt with by other authors using ligand field theory [2, 3]. For both compounds the differences between the measured and the calculated quadrupole …
Electronic and optical properties of pristine, N- and S-doped water-covered TiO2 nanotube surfaces
2019
For rational design and improvement of electronic and optical properties of water-splitting photocatalysts, the ability to control the band edge positions relative to the water redox potentials and the photoresponse as a function of environmental conditions is essential. We combine ab initio molecular dynamics simulations with ab initio many-body theoretical calculations to predict the bandgap and band edge energies, as well as the absorption spectrum of pristine and N- and S-doped TiO2 nanotubes using the DFT+U and G0W0 approaches. Both levels of theory show similar trends, and N+S-codoping appears to be the optimal system for photocatalytic water splitting both in dry and humid conditions…
Nanostructured electrodes for hydrogen production in alkaline electrolyzer
2018
Abstract Ever-widespread employment of renewable energy sources, such as wind and sun, request the simultaneous use of effective energy storage systems owing to the intermittent and unpredictable energy generation by these sources. The most reliable storage systems currently under investigation are batteries and electrochemical cells for hydrogen production from water splitting. Both systems store chemical energy which can be converted on demand. The low power density is the weakness of the batteries while the high production cost limits currently the wide use of hydrogen from electrochemical water splitting. In this work, attention was focused on the use of nanostructured Ni as a cathode f…
Novel TiO2-WO3 self-ordered nanotubes used as photoanodes: Influence of Na2WO4 and H2O2 concentration during electrodeposition
2021
[EN] Hybrid TiO2-WO3 nanostructures has been synthesized by electrochemical anodization under controlled hydrodynamic conditions followed by electrodeposition in the presence of different contents of Na2WO4 (5, 15 and 25 mM) and H2O2 (20, 30 and 40 mM). The influence of the electrolyte used for electrodeposition on the morphology, crystalline structure and photoelectrochemical response for water splitting has been evaluated through Field Emission Electronic Microscopy, High-Resolution Transmission Electron Microscopy, Confocal Raman Spectroscopy, Grazing Incidence X Ray Diffraction, X-Ray Photoelectron Spectroscopy, Atomic Force microscopy and photocurrent versus potential measurements. Add…
Photocatalytic H2 production over inverse opal TiO2 catalysts
2019
Abstract The influence of BiVO4 and CuO on the chemico-physical properties of TiO2-based systems is reported. The performances of these systems were investigated in the photocatalytic H2 production both under UV and solar light irradiation. The characterization data pointed out that the obtained TiO2 samples have highly porous inverse opal structures with interconnected macropores. Inverse opal TiO2 exhibited higher activity in the H2 production than the commercial TiO2 due to the peculiar porosity that allows photons to enter inside the photocatalyst. A further improvement in terms of photoactivity was verified by addition of increasing amounts of BiVO4. On the contrary a small CuO content…