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91.
92.
Summary Dipole polarizability estimates at have been calculated for the 2p and 3p open-shell negative ions in their ground and valence excited states. To complete the sequence such estimates for F– and Cl– in their ground1
S state have also been made. Single configuration based linear response theory has been adopted presently with a view to study the effect of RPA-type correlations on the polarizabilities of such systems. For the 3p open-shell systems the innermost 1s core has been kept frozen. Most of the results are reported for the first time. Agreement with existing data, wherever available, is reasonable. The convergence of the polarizability estimates towards basis sets has been studied. 相似文献
93.
The progress of high temperature processes is generally described in terms of variation of the degree of conversion () with time (t). The present paper outlines a procedure for making use of-t plots for comparative assessment of productivity and energy requirements for a test system with respect to a reference, on the basis of some simplifying assumptions. It is assumed that the throughput is inversely proportional to reaction time as in the case of batch reactors and plug flow reactors. It is also assumed that the energy requirement is a simple function of process temperature. The principles outlined is illustrated with reference to some laboratory data for reduction of iron oxide by coal.The authors wish to thank Prof. P. R. Rao, Director National Metallurgical Laboratory, Jamshedpur, India, for providing facilities for experimental work and for according permission to publish this work. 相似文献
94.
Armstrong TA Bettoni D Bharadwaj V Biino C Borreani G Broemmelsiek D Buzzo A Calabrese R Ceccucci A Cester R Church M Dalpiaz P Dalpiaz PF Dibenedetto R Dimitroyannis D Fabbri MG Fast J Gianoli A Ginsburg CM Gollwitzer K Hahn A Hasan M Hsueh S Lewis R Luppi E Macrí M Majewska AM Mandelkern M Marchetto F Marinelli M Marques J Marsh W Martini M Masuzawa M Menichetti E Migliori A Mussa R Palestini S Pallavicini M Pastrone N Patrignani C Peoples J Pesando L Petrucci F Pia MG Pordes S Rapidis P 《Physical review letters》1992,69(16):2337-2340
95.
Non-isothermal studies of some adduct molecules of metallic halides with tetrahydropyran as the type MX2(THP)y in solid state, were carried out with a Derivatograph, where M Mn(II), Co(II), Ni(II), Cu(II) or Cd(II), XCl- or Br-, THPtetrahydropyran and y0.1–1. These adduct molecules lost tetrahydropyran in single or multiple steps upon heating. Thermally stable intermediate products were isolated and characterised by elemental analysis and IR spectral measurement. The activation energy for each step of decomposition of the adduct was evaluated from the analysis of TG, DTG and DTA curves of the respective derivatogram. The enthalpy change was evaluated from the DTA peak area and the order of reaction was found to be unity, for each step of decomposition. Thermal parameters for the above adducts were compared with the adducts of other oxocompounds like dioxan, tetrahydrofuran, ethylene glycol dimethyl ether and diisopropyl ether. 相似文献
96.
It is demonstrated that relatively large geometrical changes make Emsley et al.'s assumption (J Am Chem Soc (1978) 100:3303)
on the counterpoise correction for the basis set superposition error including the fragment relaxation terms unacceptable.
Received: 23 September 1997 / Accepted: 31 October 1997 相似文献
97.
Polycondensation of the diacid chloride of 2-(3-carboxy vinyl)phenyl-1,3-dioxoisoindoline-5-carboxylic acid with m-phenylenediamine and the diacid chloride of 2-(4-carboxy phenyl)-1,3-dioxoisoindoline-5-carboxylic acid with 1,5-bis(3-aminophenyl)1,4-pentadien-3-one was carried out in polar solvents to produce new unsaturated polyamide–imides. The solution and the thermal, electrical, and a few other properties of the polymers were studies. The polymers were soluble in highly polar solvents. The solubility parameter of the polymers was calculated from the Small's group contribution. The polymers were fairly thermostable and underwent crosslinking creaction when heated, preferably in the presence of a suitable catalyst. The crosslinked polymers were in soluble even in highly polar solvents and possessed higher thermal stability. The swelling behavior of the polymers was studied and the molecular weight between two consecutive crosslinks was determined. X-ray diffraction and the dielectric properties of the polymers and their crosslinked products were also studied. 相似文献
98.
Margaret A Brimble Caryn Burgess Rosliana Halim Maria Petersson Jayanta Ray 《Tetrahedron》2004,60(27):5751-5758
The uncatalyzed reaction of N-(tert-butoxycarbonyl)-2-tert-butyldimethylsilyloxypyrrole 3 with 1,4-quinones bearing an electron withdrawing group at C-2 has been studied. Use of 1,4-quinones 4, 5 bearing an ester group at C-2 provided an efficient synthesis of the respective pyrrolidinobenzofuran adduct 9 or pyrrolidinonaphthofuran adduct 10 whereas use of 1,4-quinones 6, 7 and 8 bearing an acetyl group at C-2 afforded silyloxypyrroles 11, 12 and 13 resulting from direct electrophilic substitution of the silyloxypyrrole by the electrophilic quinone. Addition of Eu(fod)3 to the reaction of 2-acetyl-1,4-naphthoquinone 7 and 3-acetyl-5-methoxy-1,4-naphthoquinone 8 with N-(tert-butoxycarbonyl)-2-tert-butyldimethylsilyloxypyrrole 3 provided a method for obtaining the pyrrolidinonaphthofuran adducts 14 and 15 together with silyloxypyrroles 12 and 13. Oxidative rearrangement of pyrrolidinonaphthofuran adduct 15 to pyrrolidino pyranonaphthoquinone 16 using ceric ammonium nitrate in acetonitrile provided a novel approach for the synthesis of an aza-analogue of the pyranonaphthoquinone antibiotic kalafungin. 相似文献
99.
Samik Gupta Anil Kumar Barik Sachindranath Pal Arijit Hazra Somnath Roy Ray J. Butcher Susanta Kumar Kar 《Polyhedron》2007
Four cis-dioxomolybdenum complexes of general formula [MoO2(Ln)EtOH] (n = 1–4) and one oxomolybdenum(IV) complex [MoO(L4)EtOH], with potentially tridentate Schiff bases derived from 5-methyl pyrazole-3-carbohydrazide and salicylaldehyde/substituted salicylaldehyde/o-hydroxy acetophenone have been prepared. The Mo(IV) complex is derived from the Mo(VI) dioxo complex by oxotransfer reaction with PPh3. The complexes are characterized by elemental analysis, electronic spectra, IR, 1H NMR, and by cyclic voltammetry. All the Mo(VI) species are crystallographically characterized. The complexes have a distorted octahedral structure in which the ligand behaves as a binegative donor one, leaving the pyrazole –N uncoordinated towards the metal center. It is also revealed from the crystal structure that the Mo(VI) center enjoys an NO5 donor environment. 相似文献
100.
Bill E Bothe E Chaudhuri P Chlopek K Herebian D Kokatam S Ray K Weyhermüller T Neese F Wieghardt K 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,11(1):204-224
The bidentate ligands N-phenyl-o-phenylenediamine, H(2)((2)L(N)IP), or its analogue 2-(2-trifluoromethyl)anilino-4,6-di-tert-butylphenol, ((4)L(N)IP), react with [Co(II)(CH(3)CO(2))(2)]4H(2)O and triethylamine in acetonitrile in the presence of air yielding the square-planar, four-coordinate species [Co((2)L(N))(2)] (1) and [Co((4)L(O))(2)] (4) with an S=1/2 ground state. The corresponding nickel complexes [Ni((4)L(O))(2)] (8) and its cobaltocene reduced form [Co(III)(Cp)(2)][Ni((4)L(O))(2)] (9) have also been synthesized. The five-coordinate species [Co((2)L(N))(2)(tBu-py)] (2) (S=1/2) and its one-electron oxidized forms [Co((2)L(N))(2)(tBu-py)](O(2)CCH(3)) (2 a) or [Co((2)L(N))(2)I] (3) with diamagnetic ground states (S=0) have been prepared, as has the species [Co((4)L(O))(2)(CH(2)CN)] (7). The one-electron reduced form of 4, namely [Co(Cp)(2)][Co((4)L(O))(2)] (5) has been generated through the reduction of 4 with [Co(Cp)(2)]. Complexes 1, 2, 2 a, 3, 4, 5, 7, 8, and 9 have been characterized by X-ray crystallography (100 K). The ligands are non-innocent and may exist as catecholate-like dianions ((2)L(N)IP)(2-), ((4)L(N)IP)(2-) or pi-radical semiquinonate monoanions ((2)L(N)ISQ)(*) (-), ((4)L(N)ISQ)(*) (-) or as neutral benzoquinones ((2) L(N)IBQ)(0), ((4) L(N)IBQ)(0); the spectroscopic oxidation states of the central metal ions vary accordingly. Electronic absorption, magnetic circular dichroism, and EPR spectroscopy, as well as variable temperature magnetic susceptibility measurements have been used to experimentally determine the electronic structures of these complexes. Density functional theoretical (DFT) and correlated ab initio calculation have been performed on the neutral and monoanionic species [Co((1)L(N))(2)](0,-) in order to understand the structural and spectroscopic properties of complexes. It is shown that the corresponding nickel complexes 8 and 9 contain a low-spin nickel(II) ion regardless of the oxidation level of the ligand, whereas for the corresponding cobalt complexes the situation is more complicated. Spectroscopic oxidation states describing a d(6) (Co(III)) or d(7) (Co(II)) electron configuration cannot be unambiguously assigned. 相似文献