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31.
Summary A second order error bound is obtained for approximating h d
by h d
, where
is a convolution of measures andQ a compound Poisson measure on a measurable abelian group, and the functionh is not necessarily bounded. This error bound is more refined than the usual total variation bound in the sense that it contains the functionh. The method used is inspired by Stein's method and hinges on bounding Radon-Nikodym derivatives related to
. The approximation theorem is then applied to obtain a large deviation result on groups, which in turn is applied to multivariate Poisson approximation.Research of the second author was supported by Schweizerischer Nationalfonds 相似文献
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Transient absorption spectroscopy on electronic levels of molecules in the liquid phase is governed by population kinetics as well as rotational diffusion. The goal of transient absorption experiments has been the true level kinetics free of rotation. Moreover, to extract the rotational time from transient photodichroism experiments the knowledge of true population kinetics is instrumental. Three methods for separating rotational and level kinetics are described theoretically, and one of them is performed experimentally using a repetitive picosecond spectrometer for the measurement of rotational behaviour of fluorescein 27 in solvents of different viscosity. 相似文献
36.
Martin TC Moecks J Belooussov A Cawthraw S Dolenko B Eiden M Von Frese J Kohler W Schmitt J Somorjai R Udelhoven T Verzakov S Petrich W 《The Analyst》2004,129(10):897-901
Signatures of Bovine Spongiform Encephalopathy (BSE) have been identified in serum by means of "Diagnostic Pattern Recognition (DPR)". For DPR-analysis, mid-infrared spectroscopy of dried films of 641 serum samples was performed using disposable silicon sample carriers and a semi-automated DPR research system operating at room temperature. The combination of four mathematical classification approaches (principal component analysis plus linear discriminant analysis, robust linear discriminant analysis, artificial neural network, support vector machine) allowed for a reliable assignment of spectra to the class "BSE-positive" or "BSE-negative". An independent, blinded validation study was carried out on a second DPR research system at the Veterinary Laboratory Agency, Weybridge, UK. Out of 84 serum samples originating from terminally-ill, BSE-positive cattle, 78 were classified correctly. Similarly, 73 out of 76 BSE-negative samples were correctly identified by DPR such that, numerically, an accuracy of 94.4 % can be calculated. At a confidence level of 0.95 (alpha = 0.05) these results correspond to a sensitivity > 85% and a specificity > 90%. Identical class assignment by all four classifiers occurred in 75% of the cases while ambiguous results were obtained in only 8 of the 160 cases. With an area under the ROC (receiver operating charateristics) curve of 0.991, DPR may potentially supply a valuable surrogate marker for BSE even in cases in which a deliberate bias towards improved sensitivity or specificity is desired. To the best of our knowledge, DPR is the first and--up to now--only method which has demonstrated its capability of detecting BSE-related signatures in serum. 相似文献
37.
Remedios González-Luque Manuela Merchán Piotr Borowski Björn O. Roos 《Theoretical chemistry accounts》1993,86(6):467-476
Summary Multiconfigurational electron correlation methods have been analyzed in order to theoretically compute the electron affinity (EA) of ozone. The near-degeneracy correlation effects, which are so important in O3 and O
3
–
, have been described using complete active space (CAS) SCF wave functions. Remaining dynamic correlation effects are computed using second-order perturbation theory (the CASPT2 method). The best calculated adiabatic value (including zero-point energy corrections), 2.19 eV, is about 0.09 eV larger than the experimental value. Comparative studies using size-consistent coupled pair functional approaches (CPF and ACPF) have also been performed. The harmonic frequencies in O
3
–
have been determined to be: 1=992, 2=572, and 3=879 cm–1, which gives a zero-point energy of 0.151 eV. 相似文献
38.
Thermal analysis,state transitions and food quality 总被引:3,自引:0,他引:3
Thermal properties of food systems are important in understanding relationships between food properties and changes in food quality. Concentrated food systems (low-moisture and frozen foods) are seldom in an equilibrium state and they tend to form amorphous, non-crystalline structures. Several glass transition-related changes in such foods affect stability, e.g., stickiness and caking of powders, crispness of snack foods and breakfast cereals, crystallisation of amorphous sugars, recrystallisation of gelatinised starch, ice formation and recrystallisation in frozen foods and rates of non-enzymatic browning and enzymatic reactions. Relationships between glass transition, water plasticisation and relaxation times can be shown in state diagrams. State diagrams are useful as stability or quality maps and in the control of rates of changes in food processing and storage.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献
39.
Heat conduction, convection and radiolysis of the
The calorimeter allows the water absorbed dose, a measure of radiotherapy, to be measured according to its definition. Different detector types are used in the PTB calorimeter; this paper discusses heat conduction, convection and the radiolysis of the
system for a ‘sealed’ detector. The ‘sealed’ detector allows the calorimeter to be operated at room temperature in the case of 60Co-γ-radiation. 相似文献
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40.
Miral Dizdaroglu Dieter Henneberg Clemens Von Sonntag 《Journal of mass spectrometry : JMS》1974,8(1):335-345
Aldoses, ketoses, deoxy-aldoses, deoxy-keto-aldoses, lactones, deoxy-lactones and other similar compounds are readily reduced by NaBD4 to the corresponding polyalcohol. Their trimethylsilyl ethers show characteristic mass spectra which allow firm assignments of the position of deuteration and hence of the nature of the starting sugar compound. The g.c./m.s. coupling technique even allows trace analysis since full information can be derived from the most intense fragments of the mass spectra. 相似文献