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951.
Aharon Givan Aharon Loewenschuss Claus J. Nielsen Mark Rozenberg 《Journal of Molecular Structure》2007,830(1-3):21-34
The FT infrared spectrum in the 4000–400 cm−1 range of SO3 vapors, matrix isolated in argon and in water doped argon solid layers, is reported. Vibrational bands are assigned to pure SO3 monomeric and polymeric species and to SO3H2O complexes, on the basis of theoretical B3LYP and MP2 calculations employing the aug-cc-pVTZ basis sets. The spectroscopic evidence suggests that in addition to the monomer, both the dimeric and the cyclic trimeric (SO3)n complexes are the only other SO3 forms present in the matrix. The spectra also indicate the presence of the 1:1 and the 1:2 SO3·H2O complexes as well as traces of H2S2O7 and water complexed H2SO4, but no evidence for a stable 2:1 SO3H2O complex was found. The occurrence of the various species is discussed in the light of their calculated energies. 相似文献
952.
An optimization scheme for atomic cluster structures, based on exaggerating the importance of the gravitational force, is introduced. Results are presented for calculations on Lennard-Jones clusters of 13, 38, and 55 atoms, and the 13-atom Morse cluster. 相似文献
953.
Adam S. Płaziak Stefan Lis Marian Elbanowski 《Monatshefte für Chemie / Chemical Monthly》1992,123(3):225-230
Summary The mass spectra of 1:1 complexes ofEDTA with lanthanide cations (Ln=Sm, Eu, Gd, Tb or Dy) upon positive/negative LSIMS are presented. In glycerol used as a matrix, adduct-ions such as [M+H]+, [M+H+nGly]+, [2M+H]+, [2M+H+Gly]+ (positive LSIMS) or [M-H]–, [M-H+nGly]–, [2M-H]–, [2M-H+Gly]– (negative LSIMS), wheren=1–3, are formed. Reactions leading to the formation of adduct-ions are suggested.
Positive/negative Liquid-Sekundärionen-Massenspektrometrie vonLn-EDTA-(1:1)-Komplexen. Bildung von molekularen Ionenaddukten mit neutralen Spezies aus der Matrix oderLn-EDTA
Zusammenfassung Die Massenspektren von 1:1-Komplexen vonEDTA mit Lanthanidenkationen (Ln=Sm, Eu, Gd, Tb oder Dy) mittels positiver/negativer LSIMS werden präsentiert. In Glycerin als Matrix bilden sich Adduktionen wie [M+H]+, [M+H+nGly]+, [2M+H]+, [2M+H+Gly]+ (positive LSIMS) oder [M-H]–, [M-H+nGly]–, [2M-H]–, [2M-H+Gly]– (negative LSIMS), wobein=1–3. Es werden Reaktionen vorgeschlagen, die zur Bildung von Adduktionen führen.相似文献
954.
Furusawa N 《Analytical and bioanalytical chemistry》2004,378(8):2004-2007
A method for the determination of aldrin, dieldrin, DDT, DDE, and DDD contamination in animal fats (beef tallow, lard, and chicken fat) without using toxic reagents is developed, that uses high-performance liquid chromatography after the sample has been prepared by matrix solid-phase dispersion (MSPD) with acidic alumina oxide. A reversed-phase C1-silica column with a mobile phase of 50% (v/v) ethanol solution (in water) and a photo-diode array detector were used for the determination. Average recoveries of the target compounds (0.2–5.0 g g–1) ranged from 84–98%, with coefficients of variation of <5%. The limits of quantitation were 0.16 g g–1 for AD, 0.10 g g–1 for DD, 0.06 g g–1 for DDT, 0.07 g g–1 for DDE, and 0.05 g g–1 for DDD. No toxic reagents were used at all. 相似文献
955.
This paper presents a parametric linear complementarity technique for the computation of equilibrium prices in a single commodity spatial model. We first reformulate the model as a linear complementarity problem and then apply the parametric principal pivoting algorithm for its solution. This reformulation leads to the study of an arc—arc weighted adjacency matrix associated with a simple digraph having weights on the nodes. Several basic properties of such a matrix are derived. Using these properties, we show how the parametric principal pivoting algorithm can be greatly simplified in this application. Finally, we report some computational experience with the proposed technique for solving some large problems. 相似文献
956.
Chunming Zhang Yu Han Shengji Jia 《Journal of computational and graphical statistics》2016,25(1):123-143
This article concerns statistical estimation of the partially linear model (PLM) for time course measurements, which are temporally correlated and allow multiple-runs for repeated measurements to enhance experimental accuracy without extending the number of time points within each trial. Such features arise naturally from biomedical data, for example, in brain fMRI, and call for special treatment beyond classical methods in either a purely nonparametric regression model or a PLM with independent errors. We develop a stepwise procedure for estimating the parametric and nonparametric components of the multiple-run PLM and making inference for parameters of interest, adaptive to either single- or multiple-run, in the presence of error temporal dependence. Simulation study and real fMRI data applications illustrate the computational simplicity and effectiveness of the proposed methods. Supplementary material for this article is available online. 相似文献
957.
Dr. Melania Prado Merini Dr. Tim Schleif Prof. Dr. Wolfram Sander 《Angewandte Chemie (International ed. in English)》2023,62(44):e202309717
Heavy-atom tunneling limits the lifetime and observability of bicyclo[4.1.0]hepta-2,4,6-triene, a key intermediate in the rearrangement of phenylcarbene. Bicyclo[4.1.0]hepta-2,4,6-triene had been proposed as the primary intermediate of the rearrangement of phenylcarbene, but despite many efforts evaded its characterization even in cryogenic matrices. By introducing fluorine substituents into the ortho-positions of the phenyl ring of phenylcarbene, the highly strained cyclopropene 1,5-difluorobicyclo[4.1.0]hepta-2,4,6-triene becomes stable enough to be characterized in argon matrices. However, even at 3 K this cyclopropene is only metastable and rearranges via heavy-atom tunneling to the corresponding cycloheptatetraene. Calculations suggest that fluorination is necessary to slow down the tunneling rearrangement of the bicycloheptatriene. The parent bicycloheptatriene rapidly rearranges via heavy-atom tunneling and therefore cannot be detected under matrix isolation conditions. 相似文献
958.
This paper describes an analytical method for trace element determination in bone tissues. The study of the influence of the
bone matrix showed that the addition of 25% ground bone to graphite powder with introduced impurities did not affect the analytical
signal of elements in the spectral excitation in a two-jet plasma. On basis of these investigations a method for direct multielement
analysis of bone tissues was suggested. The sample preparation procedure consisted in mixing powdered bone (particle size
30 μm or less) with a spectroscopic buffer (graphite powder plus NaCl) in ratio 1:3 or to a greater extent depending on the
analyte concentration. Reference samples based on graphite powder were used for construction of calibration curves. The NaCl
concentration in analyzed and calibration samples was 15 wt%. The effect of particle size was revealed from the determination
of Ba, Sr, and Mg. To eliminate this effect, treatment of the samples with nitric acid was proposed. The validation of the
technique was confirmed by comparison of the analysis results of a bone sample with those obtained by inductively coupled
plasma atomic emission spectrometry after wet acid digestion. The limits of detection estimated for 20 elements were the following
(μg g-1): 0.1 (Ag), 1.0 (Al), 1.0 (Ba), 0.1 (Be), 1.2 (Bi), 0.4 (Cd), 1.0 (Co), 0.2 (Cu), 0.6 (Cr), 1.9 (In), 2 (Fe), 0.3 (Ga), 0.4
(Mn), 0.4 (Mo), 0.7 (Ni), 1.0 (Pb), 0.7 (Sn), 0.8 (Tl), 5 (Sr), 1.0 (Zn). 相似文献
959.
N. Castro-González J.Y. Vélez-Cerrada 《Journal of Mathematical Analysis and Applications》2008,341(2):1213-1223
Given a bounded operator A on a Banach space X with Drazin inverse AD and index r, we study the class of group invertible bounded operators B such that I+AD(B−A) is invertible and R(B)∩N(Ar)={0}. We show that they can be written with respect to the decomposition X=R(Ar)⊕N(Ar) as a matrix operator, , where B1 and are invertible. Several characterizations of the perturbed operators are established, extending matrix results. We analyze the perturbation of the Drazin inverse and we provide explicit upper bounds of ‖B?−AD‖ and ‖BB?−ADA‖. We obtain a result on the continuity of the group inverse for operators on Banach spaces. 相似文献
960.
Ivana Djolovi? Eberhard Malkowsky 《Journal of Mathematical Analysis and Applications》2008,340(1):291-303
We establish some identities or estimates for the operator norms and Hausdorff measures of noncompactness of linear operators given by infinite matrices that map the matrix domains of triangles in arbitrary BK spaces with AK, or in the spaces of all convergent or bounded sequences, into the spaces of all null, convergent or bounded sequences, or of all absolutely convergent series. Furthermore, we apply these results to the characterizations of compact operators on the matrix domains of triangles in the classical sequence spaces, and on the sequence spaces studied in [I. Djolovi?, Compact operators on the spaces and , J. Math. Anal. Appl. 318 (2) (2006) 658-666; I. Djolovi?, On the space of bounded Euler difference sequences and some classes of compact operators, Appl. Math. Comput. 182 (2) (2006) 1803-1811]. 相似文献