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81.
The direct CI method, which avoids explicit calculation of the Hamiltonian matrix, is presented in a new form. The method is linked with Davidson's algorithm for iterative evaluation of the ground state eigenvector. The viability of the method is indicated by the test calculations on water which are described.  相似文献   
82.
The method used at LGC for analysis of “total” 19-norandrosterone (19-norandrosterone glucuronide plus “free” 19-norandrosterone) in urine for the Comité Consultatif pour la Quantité de Matière Pilot Study (CCQM-P68) is described. The analytical method used was a modified version of the method developed at the National Measurement Institute of Australia, which used a hydrolysis and derivatisation procedure first described by the German Sports University. This method is routinely used by World Anti-Doping Agency-accredited laboratories for sports drug testing. The main modifications made to the method were the use of 19-norandrosterone glucuronide as a calibration standard and 19-norandrosterone glucuronide-d4 as an isotopically labelled internal standard, and the use of a bench-top quadrupole gas chromatograph–mass spectrometer. The results produced by LGC (2.14 ± 0.15 ng g−1 expanded uncertainty, coverage factor k = 2) were in excellent agreement with those from other participating national metrology institutes and thus further validates the exact-matching isotope-dilution mass spectrometric procedures used at LGC for a wide range of reference measurement applications, including measurement of ng g−1 levels of steroids in a biological matrix.  相似文献   
83.
Isolated polyfluorobenzene (PFB) molecules and their protonated forms are investigated by the AM1 method with full geometry optimization. The proton affinities of PFB are estimated for different protonated positions. The proton affinity of PFB averaged over all isomers is shown to decrease monotonically as the number of fluorine atoms in the molecule increases. The relative populations of different isomers of arenonium ions (AI) formed by PFB protonation are determined. From the calculated data, the value of + for the F atom in theipso-position is estimated as 1.00. The activation energies of the 1,2-hydrogen shifts in AI are calculated. The dependences of the proton affinity and the activation energies of 1,2-hydrogen shifts on the number of halogen atoms are found to have distinct characters for PFB and polychlorobenzenes. The physical reasons for these difference are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1878–1882, November, 1993.  相似文献   
84.
The homotopic method has been used to analyze the kinetic model of three-stageCO oxidation on two nonuniform surface patches conjugated byCO 2 spillover. Diagrams of steady states depending on the portion of surface patchm 1 at various temperatures and pressure ratiosP(O 2)/P(CO) have been constructed. The ratios of different type patches corresponding to the maximum overall reaction rate have been found.  相似文献   
85.
To reduce the amount of hazardous chemical bottle waste in the environment, we report the optimization research of silica extraction in chemical bottle waste into silica gel. Alkali fusion and sol–gel process were utilised to prepare silica gel effectively. The alkali fusion process was carried out by adding sodium hydroxide to produce sodium silicate. Afterwards, silica gel was prepared by the sol–gel method using hydrochloric acid. Box-Behnken Design (BBD) was applied to Optimisation factors the poptimiseactors affecting the silica recovery. The factors that optimised mass ratio, particle size, and temperature. The optimum recovery of silica gel was obtained by SiO2: NaOH mass ratio of 1:3, the particle size of 63–74 µm, and a temperature of 800 °C. The purity of silica gel optimum is 63.74% characterised using X-ray fluorescence. The structure of silica gel is the appearance of amorphous peaks at 2θ 20-30° characterised using an x-ray diffractogram. The silica gel surface was characterises using scanning electron microscopy-energy dispersive x-ray. It showed an irregular surface and characteristic showed that silica gel had a radius of 15.74 nm and a specific surface area of 297.08 m2.  相似文献   
86.
We present the implementation and demonstration of the Chebyshev pseudo-spectral method coupled with an adaptive mesh method for performing fast and highly accurate electrophoresis simulations. The Chebyshev pseudo-spectral method offers higher numerical accuracy than all other finite difference methods and is applicable for simulating all electrophoresis techniques in channels with open or closed boundaries. To improve the computational efficiency, we use a novel moving mesh scheme that clusters the grid points in the regions with poor numerical resolution. We demonstrate the application of the Chebyshev pseudo-spectral method on a moving mesh for simulating nonlinear electrophoretic processes through examples of isotachophoresis (ITP), isoelectric focusing (IEF), and electromigration-dispersion in capillary zone electrophoresis (CZE) at current densities as high as 1000 A/m. We also show the efficacy of our moving mesh method over existing methods that cluster the grid points in the regions with large concentration gradients. We have integrated the adaptive Chebyshev pseudo-spectral method in the open-source SPYCE simulator and verified its implementation with other electrophoresis simulators.  相似文献   
87.
2,3,6,7-Tetrahydro-as-indacene-1,8-dione 4 was prepared in 4 steps starting from 2-methyl-furan by modification of a literature procedure. Appliance of Noyori’s asymmetric transfer hydrogenation, resulted in (1S,8S)-1,2,3,6,7,8-hexahydro-as-indacene-1,8-diol 5 in high yield (81%) and excellent enantioselectivity (>99% ee) or (8S)-8-hydroxy-3,6,7,8-tetrahydro-2H-as-indacen-1-one 6 in moderate yield (58%) and equally high enantioselectivity (98.5% ee), depending on the conditions. The asymmetric reduction was expected to yield the (S)-alcohols using the (S,S)-Ts-DPEN ligand, which was confirmed by the appliance of the exciton chirality method on the corresponding bis(p-dimethylamino)benzoate 7.  相似文献   
88.
Multireference single‐ and double‐excitation configuration interaction (MRD‐CI) calculations of transition energies for the Hg atom and spectroscopic constants for the HgH molecule are carried out with the generalized relativistic effective core potential (GRECP) method. A new selection criterium for the reference configurations is discussed. The calculated spectroscopic constants are compared with experimental data and results of calculations of other groups. Improvement of accuracy is mainly observed for bond lengths from the GRECP/MRD‐CI calculations (without applying the T = 0 correction) with respect to the results of other groups. Analysis of the quality of the approximations employed is carried out. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002  相似文献   
89.
Copolymerization of an excess of methyl methacrylate (MMA) relative to 2-hydroxyethyl methacrylate (HEMA) was carried out in toluene at 80 °C according to both conventional and controlled Ni-mediated radical polymerizations. Reactivity ratios were derived from the copolymerization kinetics using the Jaacks method for MMA and integrated conversion equation for HEMA (rMMA = 0.62 ± 0.04; rHEMA = 2.03 ± 0.74). Poly(ethylene glycol) α-methyl ether, ω-methacrylate (PEGMA, Mn = 475 g mol−1) was substituted for HEMA in the copolymerization experiments and reactivity ratios were also determined (rMMA = 0.75 ± 0.07; rPEGMA ∼ 1.33). Both the functionalized comonomers were consumed more rapidly than MMA indicating the preferred formation of heterogeneous bottle-brush copolymer structures with bristles constituted by the hydrophilic (macro)monomers. Reactivity ratios for nickel-mediated living radical polymerization were comparable with those obtained by conventional free radical copolymerization. Interactions between functional monomers and the catalyst (NiBr2(PPh3)2) were observed by 1H NMR spectroscopy.  相似文献   
90.
The Monte Carlo method has been used to simulate CO oxidation on a lattice consisting of various alternating patches: M1, where s(CO)>s(O2) and M2, where s(CO)2). The reaction is shown to proceed over all the surface at low temperature as COads spillover from M1 to M2 and backwards.  相似文献   
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