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O. G. Stradella S. A. Maluendes E. A. Castro A. H. Jubert 《Theoretical chemistry accounts》1987,72(1):57-62
By means of Bader's approach on topological properties of the electronic density, the major stability of the O-bonded adduct over the C-bonded one between MgF2 and CO is reinforced. 相似文献
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Preparation, Crystal Structure, and Normal Coordinate Analysis of Linkage Isomeric Pentachloroiodoselenocyanatoosmates(IV). Crystal Structure of trans‐(PPh4)2[OsCl4I(NCSe)] By treatment of the solution of (n‐Bu4N)2[OsCl5I] in dichloromethane with suspended Pb(SeCN)2 the linkage isomers trans‐(n‐Bu4N)2[OsCl4I(NCSe)] ( 1 ) and trans‐(n‐Bu4N)2[OsCl4I(SeCN)] ( 2 ) are formed, which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X‐Ray structure determination on a single crystal of trans‐(PPh4)2[OsCl4I(NCSe)] (triclinic, space group P1¯, a = 10.8950(13), b = 11.076(2), c = 20.980(2)Å, α = 96.940(10), β = 98.747(9), γ = 104.419(11)°, Z = 2) reveals, that the nearly linear selenocyanate group in trans position to the iodine atom is coordinated with the Os‐N‐C angle of 171.1°. Based on the molecular parameters of the X‐ray determination ( 1 ) and estimated data ( 2 ) the IR and Raman spectra of both linkage isomers are assigned by normal coordinate analysis. The valence force constants are fd(OsN) = 1.70 und fd(OsSe) = 1.15 mdyn/Å. 相似文献
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Preparation, Crystal Structure and Normal Coordinate Analysis of Linkage Isomeric Pentachlororhodanoosmates(IV) By treatment of [OsCl5I]2? with (SCN)2 in dichloromethane the linkage isomers [OsCl5(NCS)]2? and [OsCl5(SCN)]2? are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-ray structure determination on single crystals of (Ph4As)2[OsCl5(NCS)] (monoclinic, space group P21/a, a = 18.872(2), b = 11.6024(2), c = 22.786(1), β = 109.057(1)°, Z = 4) and (Ph4As)2[OsCl5(SCN)] (monoclinic, space group P21/a, a = 19.057(2), b = 11.306(2), c = 22.612(1), β = 106.64(2)°, Z = 4) reveals the complete ordering of the complex anions. The thiocyanate group is located above one of the Cl ligands of the equatorial plane with the Os? N? C angle of 166.1° for N bonding and the Os? S? C angle of 109.9° for S bonding. The IR and Raman spectra of both linkage isomers known from literature are assigned by normal coordinate analysis based on the general valence force field using the molecular parameters of the X-ray determination. The valence force constants are fd(OsN) = 1,81 and fd(OsS) = 1,32 mdyn/Å. Taking into account increments of the trans influence a good adjustment between observed and calculated frequencies is achieved. 相似文献
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Abbas Eslami 《Thermochimica Acta》2004,409(2):189-193
Solid state thermal isomerization of [Co(NH3)5(ONO)]Cl2 (nitrito isomer) to [Co(NH3)5(NO2)]Cl2 (nitro isomer) and reverse reaction were investigated by non-isothermal differential scanning calorimetry (DSC) and found to be essentially an equilibrium process. The interconversions are accelerated at above 65 °C and reach to equilibrium state at about 155 °C. After establishment of the equilibrium the relative amounts of two isomers at any temperature are governed by Gibbs free energy relationship. The experimental enthalpy changes of isomerization of pure nitrito and nitro solid samples to the equilibrium state are −4.67 (±0.19) and 0.99 (±0.05) kJ mol−1, respectively. From these values, total enthalpy change was calculated as: ΔH°=−5.66(±0.20) kJ mol−1. Using Gibbs free energy relationship, equilibrium constant, total free energy and entropy changes were estimated at 60 °C as: K=7.72(±0.8), kJ mol−1 and J K−1 mol−1.An initial rate method has been developed to determine the kinetic parameters of these reactions from non-isothermal DSC data. Both nitro to nitrito and reverse reactions obey first order kinetic law in solid state. Estimated activation parameters of forward and reverse paths at 60 °C are , , and , respectively. The negative activation entropy of both directions support the intramolecular mechanism of isomerization, including formation of a seven coordinate transition state, which formerly suggested based on spectral and X-ray methods. 相似文献
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The present study illustrated the stability of linkage isomers of [Fe(CO)4(NCS)]? and [Fe(CO)4(SCN)]? by the use of PBE quantum method. It also investigated the polarity of solvent effect on dipole moment, structural parameters, and frontier orbital energies of complexes. The results indicated that the polarity of solvent had a significant effect on the frontier orbital energies and HOMO-LUMO gap. The character of Fe-C bonds of molecules was analyzed by Natural bond orbital (NBO) analysis. Back-bonding effect in these bonds was explored with calculation of quadrupole polarization of carbon atom by QTAIM analysis. Also, 14N NQR parameters were used for the illustration of Fe-NCS and Fe-SCN bonds. 相似文献
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In a recent paper the authors introduced an infinite class of global optimization algorithms based upon random sampling from the feasible region and local searches started from selected sample points, based upon an acceptance/rejection criterion. All of the algorithms of that class possess strong theoretical properties.Here we analyze a member of that family, which, although being significantly simpler to implement and more efficient than the well known Multi-Level Single-Linkage algorithm, enjoys the same theoretical properties. It is shown here that, with very high probability, our method is able to discover from which points Multi-Level Single-Linkage will decide to start local search. 相似文献
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合成了 trans-PtHX(AsPh_3)_2(X=Cl~-、Br~-、I~-、SCN~-)四个配合物,除 trars-PtHCl(AsPh_3)_2外,其余三个为新配合物。用 NMR 和 IR 谱鉴定了结构和 trans-PtHSCN(AsPh_3)_2 的键合异构。研究了配体(X)对铂-氢化学位移(δ_H)和铂-氢偶合常数(J_(Pt-H))的影响、铂-氢键键长与铂-氢化学位移(δ_H)的关系以及铂-氢化学位移(δ_H)与铂-氢伸展振动频率的相关性。发现 trans-PtHCl(AsPh_3)_2 在不同溶剂中的重结晶产物,其 Pt-H 键的红外伸展振动频率不同,而 ~1HNMR 谱(在 CDCl_3 中)完全一样。 相似文献
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Let be an integral projective curve. One defines the speciality index e(C) of C as the maximal integer t such that , where ω
C
denotes the dualizing sheaf of . Extending a classical result of Halphen concerning the speciality of a space curve, in the present paper we prove that
if is an integral degree d curve not contained in any surface of degree < s, in any threefold of degree < t, and in any fourfold of degree < u, and if , then Moreover equality holds if and only if C is a complete intersection of hypersurfaces of degrees u, , and . We give also some partial results in the general case , .
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