Stretching vibrations and structure of (HF) n (n=4–8) clusters

IR spectra of 24 structural isomers of (HF) _n (n=4–8) clusters were calculated in the framework of semiempirical theory of polyatomic molecule vibrations. Based on the results obtained and available experimental data it is proposed that (HF) _n associates comprising 3–5-membered cycles with attached monomeric HF units are present in molecular beams and gas phase.Ab initio calculations performed by the SCF method show the existence of local minima corresponding to such structures on the potential energy surface of (HF) _n clusters (n=4–6). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 435–443, March, 1997.     

Crystal and molecular structure of 1-(trimethylsilylmethyl)benzotriazole

The crystal and molecular structure of 1-(trimethylsilylmethyl)benzotriazole has been established by X-ray diffraction (XRD) analysis. The coordination polyhedron of the silicon atom in this molecule is a tetrahedron. The bond lengths and angles of the 1-(trimethylsilylmethyl)benzotriazole molecule were compared with those of related crystal structures.     

Characterization of phase transition of Ba2-xSrxIn2O5 by thermal analysis and high temperature X-ray diffraction

The phase transitions of Ba_2-xSr_xIn₂O₅ were investigated with various thermal analyses and high-temperature X-ray diffraction. It was clarified that crystal structure of Ba_2-xSr_xIn₂O₅ with x=0.0~0.4 varies from brownmillerite through distorted perovskite to another distorted perovskite with increase of temperature. The phase transition from brownmillerite to distorted perovskite was revealed to be first order, whereas transition from distorted perovskite to another one was second order. The specimen with x≥0.5 showed only one first order phase transition from brownmillerite to distorted perovskite. The phase diagram of Ba_2-xSr_xIn₂O₅ was established and existence of tricritical point at ~1100°C with x=0.4~0.5 was suggested. This revised version was published online in August 2006 with corrections to the Cover Date.     

Assignment of acetyl groups to O-2 and/or O-3 of pectic oligogalacturonides using negative electrospray ionization ion trap mass spectrometry

Partially acetylated and methylated oligogalacturonides produced by enzymatic hydrolysis of sugar beet pectin were analysed by negative electrospray ionization ion trap mass spectrometry (ESI-ITMS). The (18)O labelling of the oligomer reducing end allowed the precise assignment of the fragments resulting from glycosidic bond and cross-ring cleavages. The collisional-induced dissociation of the C(i) and Z(j) fragment ions through sequential MS(n) experiments always displayed (0, 2)A-type cross-ring cleavage ions which were related to C(2)H(4)O(2) losses. These (0, 2)A ions appeared to be highly diagnostic ions allowing the precise location of the acetyl groups to the O-2 and/or O-3 of the acetylated galacturonic acid residues.     

乙烯在纳米催化剂InVO4-TiO2上的可见光降解

The InVO₄-TiO₂ nano-crystalline photocatalyst was prepared by sol-gel method and characterized by DRS, FTIR, Raman and XRD. The photocatalytic activities of the prepared sample were investigated by photocatalytic degradation of ethylene in the gaseous phase under visible light irradiation (λ>450 nm). The results indicate that both of pure TiO₂ and InVO₄ or their simple mixture show no photocatalytic activities for degradation of ethylene under visible light irradiation. However, as-synthesized InVO₄-TiO₂ catalyzes the degradation of ethylene into CO₂ under visible light irradiation. In addition, the interaction between InVO₄ and TiO₂ results in some structural distortion to all the crystal forms of TiO₂ in as-synthesized catalyst InVO₄-TiO₂.     

脂肪胺结构与密度和折光指数关系的探讨

本文用拓扑方法探讨了脂肪胺的密度和折光指数与其分子结构之间的关系。提出一个既适用于密度又适用于折光指数的定量关系。应用这一定量关系, 不仅能够描述脂肪胺密度和折光指数的变化规律。预测脂肪胺的密度和折光指数,而且能够合理表征物质结构与性能之间的关系。     

Finite-size scaling study of a first-order temperature-driven symmetry-breaking structural phase transition

We present a study of finite-size effects in a model exhibiting a first-order temperature-driven symmetry-breaking structural phase transition in theL × cylindrical geometry in theL limit. Exact studies demonstrate the applicability of our scaling ansatz even in the one-dimensional limit, making this model ideal for studying finite-size effects. The scaling ansatz, similar to the previously developed ansatz for field-driven transitions, demonstrates that latent heat is crucial in driving these transitions. This ansatz is supported by a 2×2 phenomenological transfer matrix based upon the symmetries of the system; this produces an analytic free energy which has the scaling form. Order parameter probability distributions show that the high- and low-temperature phases coexist only in a small finite-size-affected regime near the bulk transition temperature; this regime vanishes exponentially fast asL diverges.     

Hexacyanometalate molecular chemistry: di-, tri-, tetra-, hexa- and heptanuclear heterobimetallic complexes; control of nuclearity and structural anisotropy

Following a bottom-up approach to nanomaterials, we present a rational synthetic route to high-spin and anisotropic molecules based on hexacyanometalate [M(CN)(6)](3-) cores. Part 1 of this series was devoted to isotropic heptanuclear clusters; herein, we discuss the nuclearity and the structural anisotropy of nickel(II) derivatives. By changing either the stoichiometry, the nature of the terminal ligand, or the counterion, it is possible to tune the nuclearity of the polynuclear compounds and therefore to control the structural anisotropy. We present the synthesis and the characterisation by mass spectrometry, X-ray crystallography and magnetic susceptibility of bi-, tri-, tetra-, hexa- and heptanuclear species [M(CN)(n)(CN-M'L)(6-n)](m+) (with n=0-5; M=Cr(III), Co(III), M'=Ni(II); L=pentadentate ligand). Thus, with M=Cr(III), d(3), S=3/2, a dinuclear complex [Cr(III)(CN)(5)(CN-NiL(n))](9+), (L(n)=polydentate ligand) was built and characterised, showing a spin ground state, S(G)=5/2, with a ferromagnetic interaction J(Cr,Cu)=+18.5 cm(-1). With M=Co(III) (d(6), S=0) were built di-, tri-, tetra-, hexa and hepanuclear CoNi species: CoNi, CoNi(2), CoNi(3), CoNi(5) and CoNi(6). By a first approximation, they behave as one, two, three, five and six isolated nickel(II) complexes, respectively, but more accurate studies allow us to evaluate the weak antiferromagnetic coupling constant between two next-nearest neighbours M'-Co-M'.     

Tantalum(v) oxoalkoxides. Synthesis and structure

Anodic oxidation of tantalum in isopropyl alcohol or prolonged reflux of an alcohol solution of Ta(OPrⁱ)₅ afford crystalline oxoisopropoxide Ta₂O(OPrⁱ)₈ · PrⁱOH (1). In its molecule, two octahedra about Ta atoms are linkedvia the shared edge [(OPrⁱ)O]. Compound1 is the first example of oxoalkoxide containing such a small number of metal atoms. Unlike the known polynuclear molecules M _n O _m (OR) _p , oxoalkoxide1 is stable in solutions; on transition to the gas phase, this compound is desolvated to form a very stable molecule Ta₂O(OPrⁱ)₈ (apparently, consisting of two octahedra with a shared edge). According to the data of mass spectrometry, analogous molecules exist in the gas phase over Ta(OAlk)₅ (Alk = Me, Et, Prⁱ, or Bu¹¹). When compound1 is heated invacuo (10^–2–10^–3 Torr), Ta(OPrⁱ)₅ is sublimated. Crystals of Ta₇O₉(OPrⁱ)₁₇ (2) were formed upon prolonged storage of solutions of1 in PrⁱOH. Heptanuclear molecule2 consists of two [Ta₄] tetrahedra with a shared vertex. These tetrahedra are additionally linked togethervia one ₃-oxo and two ₂-OPrⁱ groups. Complex2 is a representative of heptameric oxoalkoxides of a new structural type.Deceased in I995.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 125–131, January, 1996.     

Variation of physicochemical properties in the aggregates of structual isomers

The regions of variation of density, enthalpy of formation, and detonation velocity of all of the formally possible structual isomers were determined for several molecular formulas of C,H,N,O-containing explosives. The histograms of the distribution of the structual isomers over these parameters were constructed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 859–862, May, 1995.The authors are grateful to Mrs. I. D. Solodukhina for the design of the graphical material.The work was carried out with the financial support of the Russian Foundation for Basic Research (Project No. 94-03-09323).