Towards empirical EPR parameters for characterizing V(IV) complexes

Improved empirical techniques are described for determining the solution structures (coordination numbers and ligand donor groups) of oxoV(IV) complexes from isotropic EPR parameters. These methods will enable more detailed structural information to be obtained than was available previously from such empirical correlations. Assignments of the structures of the V(IV)/oxalate complexes were found to differ from those proposed in the literature and have been important in developing the empirical parameters reported here. In acidic solutions (pH≤1), V(V) oxalate complexes decay slowly to yield three V(IV) complexes, [V(O)(ox)₂]^2?, [V(O)(ox)(OH₂)₃]⁰ andcis-[V(O)(ox)₂(OH₂)]^2? (ox=oxalato(2-)), which have been characterized by EPR spectroscopy. These same three complexes are obtained from the direct reaction of V(IV) with oxalic acid. The structures of these complexes were assigned on the basis of the pH and [oxH₂] dependences of the EPR signals and differ significantly to those reported in the literature. The equilibria among the five- and six-coordinate complexes, and the protonation/deprotonation equilibrium of the six-coordinate species are consistent with the well-studied isoelectronic Cr(V) system.     

High oxygen pressure: A new route to the stabilization of unusual oxidation states of transition elements

Abstract

High oxygen pressures have been developed these last twenty years using three main methods: compressed gas, oxidizing solution or in solid state thermal decomposition of KClO₃.

Using these different techniques and adjusting the local structural and chemical bonding characterizing the local surrounding of a transition element, unusual oxidation states [Fe(IV), Fe(V),Co(III),Co(IV),Ni(III),Cu(III)] have been stabilized in oxygen lattices derived from the (3D) perovskite or (2D)K₂NiF₄ structures.     

Beam-foil study of A1 IV and A1 V between 1100 and 1900 Å

Beam-foil spectra of aluminum have been recorded between 1100 and 1900 Å using ion energies from 0.3 to 1.5 MeV. Most of the observed lines are due to A1 IV and A1 V. First lifetime measurements have been made for 9 and 8 levels in A1 IV and A1 V, respectively.     

14N NQR study of the structural phase transitions in NH4NO3

The temperature dependences of the¹⁴N nuclear quadrupole resonance frequencies have been measured in phases II, III, IV and V of ammonium nitrate with the help of the¹H–¹⁴H nuclear quadrupole double resonance technique. The experimental results are related to the proposed crystal structures and disorder in the various crystallographic phases.     

Electrical and optical defect spectroscopy of compound semiconductors

Some aspects of recent developments in defect characterization of II–VI, III–V and IV–IV compounds are reviewed. It is shown that in addition to junction space charge techniques high-resolution spectroscopy measurements have provided complementary methods for a more detailed analysis of defects. The application of junction space charge techniques to the study of defects in Si/Ge low-dimensional structures is discussed.     

Linear carbon dioxide in the high-pressure high-temperature crystalline phase IV

High-temperature IR absorption spectra of solid CO2 in phases II and IV were measured in a resistive heated diamond anvil cell up to 30 GPa. The spectral structures of the bending mode, observed in high quality thin crystalline samples, and of the IR lattice phonons, measured for the first time between 80 and 640 K, are discussed using group theory arguments. According to this analysis the claimed bent molecular geometry of CO2 in phase IV can be unambiguously ruled out. Furthermore, the structures of both phases II and IV have been identified, among those so far proposed, as orthorhombic.     

Phase diagram of Bi up to 140 kbars

The phase diagram of Bi has been studied by resistometric techniques in the temperature range of 30 to 300°K up to pressures of 140 kbars. Using the original Bridgman phase notation, the phase transitions I–II, II–III, I–III, III–IV and V–VI were observed. Two new phases, designated VIII and IX were observed in this region. The triple points occurring between I–II–III near 29.5 kbars and 160°K, between IV–V–VIII near 55 kbars and 240°K, between V–VI–VIII near 72 kbars and 255°K and between VI–VIII–IX near 135 kbars and 250°K. Earlier measurements were adjusted to the 1970 Drickamer pressure scale and compared to the present results. A phase diagram is proposed for pressures to 140 kbars. Calculations of the volume changes and latent heats of transformation are made near the triple points I–II–III, IV–V–VIII and V–VI–VIII using the measured volume changes of Bridgman for the I–II, IV–V and V–VI transitions. The latent heat associated with the III–IV transition was calculated using the volume data of Bridgman to be less than ? 2 cal/mol.     

Production and properties of metal-carbon composite coatings with a nanocrystalline structure

It is suggested to produce metal-carbon composite coatings by magnetron sputtering of mosaic cathodes, which are Group IV, V, and VI metals. The mosaic structure of the cathode elements are computer-optimized for each of the metals. Reflection electron diffraction studies show that the coatings have the amorphous or nanocrystalline structures, which are thermally stable. The coatings offer specific physical properties, in particular, low friction factor and high hardness.     

Contribution of π-bonds to effective charges,cohesive energy,and force constants of graphene-like compounds

For 14 two-dimensional hexagonal compounds IV–IV and III–V, analytical expressions have been obtained using the Harrison bond-orbital method for the contribution from the π-interaction to the polarity of interatomic bonds, the effective atomic and transverse dynamical charges and their dependences on the deformation, as well as to the binding energy, the cohesive energy, and the central and non-central force constants.     

Mössbauer investigation of the reaction of ferrate(VI) with sulfamethoxazole and aniline in alkaline medium

Mechanisms on the oxidation of sulfamethoxazole (SMX) and aniline by ferrate(VI) (Fe^VIO $_{4}{^{2-}}$ , Fe(VI)) in alkaline medium suggested the formation of Fe(VI)-SMX or Fe(VI)-aniline intermediates, respectively. Fe(V) and Fe(IV) as other intermediate iron species have also been proposed in the mechanism. In this paper, rapid freeze Mössbauer spectroscopy was applied in rapidly frozen samples to explore intermediate iron species in the reactions of SMX and aniline with Fe(VI). In both reactions, Fe(VI)-SMX and Fe(VI)-aniline intermediates were not seen in second-minute time scale. Fe(V) and Fe(IV) were also not observed. Fe(III) was the only final species of the reactions.     

SiP化合物结构和电子特性的第一性原理研究

应用第一性原理方法研究了SiP化合物的结构和电子特性,并且将研究推广到其他第四族元素磷化物(IV-P).在研究的各种结构中,SiP单斜晶体结构是能量最低、最稳定的结构.SiP的体弹性模量比CN和CP化合物以及相对应的第三族元素氮化物和磷化物要小.SiP不同的结构间能发生相变,其单斜晶体结构(monoclinic)在压强为6.2 GPa, 15.0 GPa, 19.3 GPa, 20.0 GPa 和 10.3 GPa时分别转变成GeP型结构、Rhom.型结构、β-InS型结构、 CsCl型结构和NaCl型结构.能带计算结果显示SiP单斜晶体结构(monoclinic)和GaSe型结构是间接带隙分别为1.123 eV 和 0.123 eV的半导体,SiP其他结构则显示出金属特性.其他化学比为1:1的第四族元素磷化物(IV-P)具有相同的性质.     

Electronic structure of bond-centred hydrogen and muonium in III–V compound semiconductors: Ab initio cluster calculations

The molecular orbital model for bond-centred hydrogen or muonium in the III–V compound semiconductors is developed with the help of ab initio cluster calculations. The influence of the loss of symmetry in going from the elemental (group IV) to the compound (III–V) materials on the electronic structure is studied. The equilibrium configurations, potential energy surfaces and electronic structures of hydrogen or muonium near the bond-centred site in GaAs, GaP and InP are calculated at the ab initio HF level in the clusters Ga₄As₄H₁₈ and the corresponding one for GaP and InP using a split-valence basis set and ab initio pseudopotentials for the core orbitals. First results of the calculations using a large Ga₂₂As₂₂H₄₂ cluster are discussed. Preliminary results for InP indicate that ionization of the bond-centre defect may be considerably easier than in the other III–V compounds. which would explain why μSR-signals corresponding to the neutral Mu^* state have not been detected in this material.     

The melting of silicon nanocrystals: Submicron thin-film structures derived from nanocrystal precursors

The size-dependent melting temperature has been shown for the group IV semiconductor silicon. A cursory comparison is made between silicon nanocrystal melting and that observed in the group II–VI material Cds and the group III–V material GaAs. Particles dispersed at a number density such that there are interactions between nanocrystals are observed to sinter before size-dependent melting occurs. Using an electron beam to selectively remove an organic mask from a substrate, this phenomenon is exploited to produce thin-film structures. This work has implications in the production of nanoelectronics, nonlinear optics and solar conversion technologies.     

Beam-foil spectroscopy of Mg III–V between 100 and 450 Å

Magnesium spectra between 100 and 450 Å have been studied with the beam foil technique. The observed lines are mainly due to Mg III, IV and V. Radiative lifetimes of eight levels have been measured and are compared with theoretical data. The discrepancy between previous theoretical results for the resonance Mg III lines has lead us to calculate again the transition probabilities of the Mg III ion.     

Oxovanadium (IV) complexes of bidentate [N,O] donor Schiff-base ligands: synthesis and mesomorphism

A series of new oxovanadium(IV) Schiff-base complexes of the type [VO(L)₂], [L?=?N-(4-n-alkoxysalicylaldimine)-4′-dodecyloxyaniline, n?=?6, 8, 16, and 18] have been synthesized. The compounds were characterized by FT-IR, ¹H-NMR, ¹³C-NMR, UV-Vis, FAB-mass, and magnetic susceptibility measurements. The mesomorphic behavior of the compounds was studied by polarized optical microscopy and differential scanning calorimetry. The compounds are all highly thermally stable exhibiting smectic mesomorphism. Non-electrolytic nature of the complexes was ascertained by solution electrical conductance measurements. Cyclic voltammetry revealed a quasireversible single-electron response for VO(V)/VO(IV) couple. A ν_V=O stretching mode at ～970?cm^?1 indicates absence of any intermolecular V=O?···?V=O interactions. Density functional theory study was carried out using DMol3 at BLYP/DNP level to determine energy optimized structure revealed a distorted square pyramidal geometry for the vanadyl complexes.     

Antibacterial and Anticancer Studies of Mononuclear and Binuclear Complexes of Tellurium(IV), Tantalum(V), Selenium(IV), and Niobium(V) Urate by Spectroscopic Methods

Journal of Applied Spectroscopy - Novel tellurium(IV), tantalum(V), selenium(IV), and niobium(V) urate complexes were prepared with molar ratios 1:1 and 2:1 (metal:ligand). The uric acid (H4UA)...     

Structural classification of layered dichalcogenides of group IV B,V B and VI B transition metals

A classification of the trigonal prismatic and octahedral structures exhibited by the layered dichalcogenides of group IV B, V B and VI B metals is achieved through consideration of the relative size, polarisation of the bonding orbitals, and the ionicity of the metal-chalcogen bond. A plot of the ratio of the covalent radii of the metal and chalcogen atoms against Pauling's resonating bond ionicity is shown to successfully achieve a separation of the two structures, consistent with the primarily covalent nature of the bonds.     

The high-pressure phase diagram of ammonia dihydrate

We have investigated the P–T phase diagram of ammonia dihydrate (ADH), ND3·2D₂O, using powder neutron diffraction methods over the range 0–9 GPa, 170–300 K. In addition to the ambient pressure phase, ADH I, we have identified three high-pressure phases, ADH II, III, and IV, each of which has been reproduced in at least three separate experiments. Another, apparently body-centred-cubic, phase of ADH has been observed on a single occasion above 6 GPa at 170 K. The existence of a dehydration boundary has been confirmed where, upon compression or warming, ADH IV decomposes to a high-pressure ice phase (ice VII or VIII) and a high-pressure phase of ammonia monohydrate (AMH V or VI).     

SiP monolayers: New 2D structures of group IV–V compounds for visible-light photohydrolytic catalysts

Because of graphene and phosphorene, two-dimensional (2D) layered materials of group IV and group V elements arouse great interest. However, group IV–V monolayers have not received due attention. In this work, three types of SiP monolayers were computationally designed to explore their electronic structure and optical properties. Computations confirm the stability of these monolayers, which are all indirect-bandgap semiconductors with bandgaps in the range 1.38–2.21 eV. The bandgaps straddle the redox potentials of water at pH = 0, indicating the potential of the monolayers for use as watersplitting photocatalysts. The computed optical properties demonstrate that certain monolayers of SiP 2D materials are absorbers of visible light and would serve as good candidates for optoelectronic devices.     

三种不同的钒氧簇合物的合成和光谱研究

利用水热法合成了三种钒氧簇合物：[{Ni(phen)₂}₂V₄O₁₂]H₂O (Ⅰ),[N(CH₂CH₂)₃NH]Na(H₂O)₆{K₄(H₂O)₄ [V₁₀O₂₈]}(H₂O)₄ (Ⅱ)和[(CH₃)₄N]₆[V₁₅O₃₆Cl] (Ⅲ)。通过用FTIR, UV-Vis DRS和荧光光谱研究了它们的结构和性能的关系。FTIR研究表明,化合物的相关基团的特征振动吸收峰和其结构相关。化合物Ⅰ的固体紫外漫反射光谱在200, 230, 260和350 nm出现四个宽峰,分别对应O_t→V, O_μ→Ni,O_μ→V荷移和phen的π-π*跃迁。文章还对这三个钒氧簇合物的荧光光谱进行了研究。最后,应用Gaussian98的量子化学计算,说明化合物Ⅰ的结构特点。