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161.
162.
R. B. King 《Russian Chemical Bulletin》1993,42(8):1283-1291
Methods derived from topology and graph theory indicate that the deltahedral boranes B
n
H
n
2– and the corresponding carboranes C2Bn–2H
n
(6 n 12) may be regarded as three-dimensional delocalized aromatic systems in which surface bonding and core bonding correspond to -bonding and -bonding, respectively, in planar polygonal two-dimensional hydrocarbons CinnH
n
(n–6)+ (n=5/7). The two extreme types of topologies which may be used to model core bonding in deltahedral boranes and carboranes are the deltahedral (D
n
) topology based on the skeleton of the underlying deltahedron and the complete (K
n
) topology based on the corresponding complete graph. Analyses of the Hoffmann-Lipscomb LCAO extended Hückel computations, the Armstrong—Perkins—Stewart self-consistent molecular orbital computations, and SCF MOab initio GAUSSIAN-82 computations on B6H6
2– indicate that the approximation of the atomic orbitals by the sum of the molecular orbitals, as is typical in modernab initio computations, leads to significantly weaker apparent core bonding approximated more closely by deltahedral (D
n
) topology than by complete (K
n
) topology.This work was presented at the Workshop The Modern Problems of Heteroorganic Chemistry sponsored by the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (May 8–13, 1993).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1353–1360, August, 1993. 相似文献
163.
Guadalupe Fortuño 《Plasma Chemistry and Plasma Processing》1988,8(1):19-34
A parametric study of the etching of Si and SiO2 by reactive ion etching (RIE) was carried out to gain a better understanding of the etching mechanisms. The following fluorocarbons (FCs) were used in order to study the effect of the F-to-Cl atom ratio in the parent molecule to the plasma and the etching properties: CF4, CF3Cl, CF2Cl2, and CFCl3 (FC-14, FC-13, FC-12, and FC-11 respectively). The Si etch rate uniformity across the wafer as a function of the temperature of the wafer and the Si load, the optical emission as a function of the temperature of the load, the etch rate of SiO2 as a function of the sheath voltage, and the mass spectra for each of the FCs were measured. The temperature of the wafer and that of the surrounding Si load strongly influence the etch rate of Si, the uniformity of etching, and the optical emission of F, Cl, and CF2. The activation energy for the etching reaction of Si during CF4 RIE was measured. The etch rate of Si depends more strongly on the gas composition than on the sheath voltage; it seems to be dominated by ion-assisted chemical etching. The etching of photoresist shifted from chemical etching to ion-assisted chemical etching as a function of the F-to-Cl ratio and the sheath voltage. The etch rate of SiO2 depended more strongly on the sheath voltage than on the F-to-Cl ratio. 相似文献
164.
V. M. Zainullina V. L. Volkov N. V. Podvalnaya A. L. Ivanovskii 《Journal of Structural Chemistry》2005,46(2):340-342
The calculations of the electronic structure of layered polyvanadate K2V3O8 were made employing the spin-polarized tight-binding LMTO method. Calculated magnetic moment for K4V6O16 compound phase equals 1.97 μB. V-O interactions were established to be dominating in the chemical bonding generation in this polyvanadate according to the estimated crystal orbital overlap population. The covalent bonds V(2)-V(2) in V(2)2O7 groups and electron density localization on vanadium atoms in isolated pyramids V(1)O5 were found. 相似文献
165.
De Proft F Fowler PW Havenith RW Schleyer Pv Van Lier G Geerlings P 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(4):940-950
Current-density maps were calculated by the ipsocentric CTOCD-DZ/6-311G** (CTOCD-DZ=continuous transformation of origin of current density-diamagnetic zero) approach for three sets of inorganic monocycles: S(4) (2+), Se(4) (2+), S(2)N(2), P(5) (-) and As(5) (-) with 6 pi electrons; S(3)N(3) (-), S(4)N(3) (+) and S(4)N(4) (2+) with 10 pi electrons; and S(5)N(5) (+) with 14 pi electrons. Ipsocentric orbital analysis was used to partition the currents into contributions from small groups of active electrons and to interpret the contributions in terms of symmetry- and energy-based selection rules. All nine systems were found to support diatropic pi currents, reinforced by sigma circulations in P(5) (-), As(5) (-), S(3)N(3) (-), S(4)N(3) (+), S(4)N(4) (2+) and S(5)N(5) (+), but opposed by them in S(4) (2+), Se(4) (2+) and S(2)N(2). The opposition of pi and sigma effects in the four-membered rings is compatible with height profiles of calculated NICS (nucleus-independent chemical shifts). 相似文献
166.
Rosa M. Gomila Antonio Frontera David Quiñonero Antonio Costa 《Tetrahedron letters》2004,45(51):9387-9391
Several porphyrin dimers have been newly designed and synthesized to construct assemblies with 1,4-diazabicyclo[2.2.2]octane (DABCO) as a bidentate binding ligand. Semi empirical (AM1) and ab initio calculations have been used to study the assemblies generated by the organization of dimers and DABCO, including the computation of 1H NMR complexation-induced chemical shifts using the ab initio/GIAO methodology. The diagnostic capacity of the theoretical method has been applied to explain experimental results and geometrical features of the complexes. 相似文献
167.
A new method for refinement of 3D molecular structures by geometry optimization is presented. Prerequisites are a force field and a very fast procedure for the calculation of chemical shifts in every step of optimization. To the energy, provided by the force field (COSMOS force field), a pseudoenergy, depending on the difference between experimental and calculated chemical shifts, is added. In addition to the energy gradients, pseudoforces are computed. This requires the derivatives of the chemical shifts with respect to the coordinates. The pseudoforces are analytically derived from the integral expressions of the bond polarization theory. Single chemical shift values attributed to corresponding atoms are considered for structural correction. As a first example, this method is applied for proton position refinement of the D-mannitol X-ray structure. A crystal structure refinement with 13C chemical shift pseudoforces is carried out. 相似文献
168.
Walter M. F. Fabian Gert Kollenz Yunus Akcamur Tevfik Riza Kök Makbule Teczan Mehmet Akkurt Wolfgang Hiller 《Monatshefte für Chemie / Chemical Monthly》1992,123(3):265-275
Summary 4-Benzoyl-5-phenylfuran-2,3-dione (1) and the urethanes2 combine under loss of carbon monoxide yielding the open chain dibenzoylacetic acid derivatives3 and4. 3a, b only can be cyclized to the oxazinone5. The keto-enole tautomerism3 4 is further investigated with aid of semiempirical quantum chemical calculations, based upon the molecular geometry of3a, deduced from an X-ray study.
Frau Univ. Prof. Dr. Helga Wittmann mit den besten Wünschen zum 70. Geburtstag gewidmet. 相似文献
169.
Rita Aparecida Zoppi Maria Isabel Felisberti Marco-Aurelio De Paoli 《Journal of polymer science. Part A, Polymer chemistry》1994,32(6):1001-1008
This work describes the preparation of polypyrrole and EPDM rubber blends, PPy/EPDM, by the sorption of pyrrole (vapor phase) in an EPDM matrix containing CuCl2. We investigated the effect of the oxidant particle-size on the sorption and polymerization equilibrium, electrical conductivity, and mechanical properties of the blends. Independently of the CuCl2 concentration and polymerization time, the polypyrrole weight fraction in the blend, Xppy, increases when the oxidant particle-size in changed from 150–250 μm to smaller than 106 μm. For blends containing 50 phr of CuCl2, obtained following 72 h of exposure to pyrrole, an increase in the Young's Modulus (from 2.2 ± 0.2 to 3.9 ± 0.6 MPa) and an increase in the electrical conductivity (from 10?9 to 10?7 S cm?1) was observed when the oxidant particle-size was decreased. Infrared spectroscopy, thermogravimetric analysis, scanning differential calorimetry, and scanning electron microscopy were used in sample characterization. © 1994 John Wiley & Sons, Inc. 相似文献
170.
Guillermo Restrepo Eugenio J. Llanos Héber Mesa 《Journal of mathematical chemistry》2006,39(2):401-416
We carried out a mathematical study of 72 chemical elements taking advantage of the chemotopological method. We selected 128
properties to define the elements (physico-chemical, geochemical and chemical properties). Then, we looked for correlated
properties and we reduced the number of them to 90. In this way we defined each element as a 90-tuple. Afterwards, we applied
principal component analysis and cluster analysis (4 similarity functions and 5 grouping methodologies). Then, we calculated
a consensus tree for the 20 dendrograms generated by the CA. Afterwards, we extracted the similarity relationships from the
consensus tree and built up a basis for a topology on the set of chemical elements. Finally, we calculated some topological
properties (closures, derived sets, boundaries, interiors and exteriors) of several subsets of chemical elements. We found
that alkali metals, alkaline earth metals and noble gases appear not related to the rest of the elements. Also, we found that
the boundary of non-metals are the semimetals with a stair-shape on the periodic table 相似文献