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21.
Joel Tellinghuisen 《Journal of Molecular Spectroscopy》2004,226(2):137-145
Heavily overlapped, or congested spectra often display much structure but few individual “lines.” Methods have been devised for analyzing such spectra through nonlinear least-squares fitting of the intensity as a function of wavelength or wavenumber. Such total spectrum fitting (TSF) methods are examined statistically for a simple diatomic model and compared with the standard “measure-assign-fit” (MAF) approach in use since the dawn of spectroscopy. Monte Carlo computations on typically 1000 synthetic spectra at a time verify that the predictions of the variance-covariance matrix are reliable under many circumstances. However in regions where the P and R branches double up, the predicted standard errors in the key spectroscopic constants rise sharply and greatly exceed estimates from the Monte Carlo ensemble statistics. In the same regions, the MAF method actually gives better precision. However, for imperfectly overlapped R and P branches, the MAF standard errors are typically three times larger than the TSF values; moreover, the MAF statistical errors are dwarfed by bias. The TSF approach, while clearly superior in these tests, has a practical drawback: it, too, can give significant bias if the spectra are analyzed with an incorrect model, as illustrated here through calculations employing the wrong function to describe the spectral lineshape. 相似文献
22.
Preparation and Molecular Structures of Oligofunctional Dirhenium Carbonyl Derivatives from Dirhenium Nonacarbonylphosphane Starting with dirheniumdecacarbonyl, one CO-Ligand was eliminated oxidatively and substituted by the labile acetonitrile ligand. As an intermediate eq-Re2(CO)9NCCH3 was received. The reaction of this labilised carbonyl with tris(trimethylsilyl)phosphine and subsequent methanolysis gave ax-Re2(CO)9PH3, which was isolated and characterized for the first time. Photochemical and thermal reaction of ax-Re2(CO)9PH3 led to the new bi- and trinuclear complexes Re2(μ-H)(μ3-PHRe(CO)5)(CO)8, Re2(μ-PH2)2(CO)8 and Re2(μ-H) · (μ-PH2)(CO)8, which were characterized by IR-, 1H- and 31P-NMR spectroscopy. The structures of ax-Re2(CO)9PH3, Re2(μ-H)(μ3-PHRe(CO)5)(CO)8 and Re2(μ-PH2)2(CO)8 were confirmed by single-crystal X-ray analysis. ax-Re2(CO)9PH3 has a very short Re? P bond length of 228(2) pm. 相似文献
23.
Véronique Cariou 《Computational Statistics》2006,21(2):325-341
Summary Several data can be presented as interval curves where intervals reflect a within variability. In particular, this representation
is well adapted for load profiles, which depict the electricity consumption of a class of customers. Electricity load profiling
consists in assigning a daily load curve to a customer based on their characteristics such as energy requirement. Within the
load profiling scope, this paper investigates the extension of multivariate regression trees to the case of interval dependent
(or response) variables. The tree method aims at setting up simultaneously load profiles and their assignment rules based
on independent variables. The extension of multivariate regression trees to interval responses is detailed and a global approach
is defined. It consists in a first stage of a dimension reduction of the interval response variables. Thereafter, the extension
of the tree method is applied to the first principal interval components. Outputs are the classes of the interval curves where
each class is characterized both by an interval load profile (e.g. the class prototype) and an assignment rule based on the
independent variables. 相似文献
24.
This paper describes the k-means range algorithm, a combination of the partitional k-means clustering algorithm with a well known spatial data structure, namely the range tree, which allows fast range searches. It offers a real-time solution for the development of distributed interactive decision aids in e-commerce since it allows the consumer to model his preferences along multiple dimensions, search for product information, and then produce the data clusters of the products retrieved to enhance his purchase decisions. This paper also discusses the implications and advantages of this approach in the development of on-line shopping environments and consumer decision aids in traditional and mobile e-commerce applications. 相似文献
25.
There is a general interest in ranking schemes applied to complex entities described by multiple attributes. Published rankings
for universities are in great demand but are also highly controversial. We compare two classification and ranking schemes
involving universities; one from a published report, ‘Top American Research Universities’ by the University of Florida's TheCenter and the other using DEA. Both approaches use the same data and model. We compare the two methods and discover important equivalences.
We conclude that the critical aspect in classification and ranking is the model. This suggests that DEA is a suitable tool
for these types of studies. 相似文献
26.
Renato Bruni 《Annals of Operations Research》2007,150(1):79-92
The paper is concerned with the problem of binary classification of data records, given an already classified training set
of records. Among the various approaches to the problem, the methodology of the logical analysis of data (LAD) is considered.
Such approach is based on discrete mathematics, with special emphasis on Boolean functions. With respect to the standard LAD
procedure, enhancements based on probability considerations are presented. In particular, the problem of the selection of
the optimal support set is formulated as a weighted set covering problem. Testable statistical hypothesis are used. Accuracy
of the modified LAD procedure is compared to that of the standard LAD procedure on datasets of the UCI repository. Encouraging
results are obtained and discussed. 相似文献
27.
Francisco Marco-Serrano 《Annals of Operations Research》2006,145(1):167-181
Managerial efficiency within the performing arts programming can be understood as the technical efficiency of transforming the resources cultural managers have available into a determined cultural output. Through this explanation different conceptions on the finished performance product it leads us to select two different output variables (number of performances, and number of attendances). In this way, three different models are considered regarding those conceptual points of view. Data on the Circuït Teatral Valencià, a Spanish regional theatres network, is used to develop empirically the concept of Managerial Efficiency and set up a framework to allow us to monitor it. 相似文献
28.
Mathematical Diagnostics (MD) deals with identification problems arising in different practical areas. Some of these problems
can be described by mathematical models where it is required to identify points belonging to two or more sets of points. Most
of the existing tools provide some identification rule (a classifier) by means of which a given point is assigned (attributed)
to one of the given sets. Each classifier can be viewed as a virtual expert. If there exist several classifiers (experts),
the problem of evaluation of experts’ conclusions arises. In the paper for the case of supervised classification the method
of virtual experts (the VE-method) is described. Based on this method, a generalized VE method is proposed where each of the
classifiers can be chosen from a given family of classifiers. As a result, a new optimization problem with a discontinuous
functional is stated. Examples illustrating the proposed approach are provided.
The work of the second author was supported by the Russian Foundation for Fundamental Studies (RFFI) under Grant No 03-01-00668. 相似文献
29.
I. Esteban-Díez 《Analytica chimica acta》2006,555(1):84-95
Orthogonal WAVElet correction (OWAVEC) is a pre-processing method aimed at simultaneously accomplishing two essential needs in multivariate calibration, signal correction and data compression, by combining the application of an orthogonal signal correction algorithm to remove information unrelated to a certain response with the great potential that wavelet analysis has shown for signal processing. In the previous version of the OWAVEC method, once the wavelet coefficients matrix had been computed from NIR spectra and deflated from irrelevant information in the orthogonalization step, effective data compression was achieved by selecting those largest correlation/variance wavelet coefficients serving as the basis for the development of a reliable regression model. This paper presents an evolution of the OWAVEC method, maintaining the first two stages in its application procedure (wavelet signal decomposition and direct orthogonalization) intact but incorporating genetic algorithms as a wavelet coefficients selection method to perform data compression and to improve the quality of the regression models developed later. Several specific applications dealing with diverse NIR regression problems are analyzed to evaluate the actual performance of the new OWAVEC method. Results provided by OWAVEC are also compared with those obtained with original data and with other orthogonal signal correction methods. 相似文献
30.
Hong Tao Gao Dong Mei Dai Tong Hua Li 《中国化学快报》2007,18(4):495-498
Non-negative matrix factorization(NMF)is a technique for dimensionality reduction by placing non-negativity constraints onthe matrix.Based on the PARAFAC model,NMF was extended for three-dimension data decomposition.The three-dimension non-negative matrix factorization(NMF3)algorithm,which was concise and easy to implement,was given in this paper.The NMF3algorithm implementation was based on elements but not on vectors.It could decompose a data array directly without unfolding,which was not similar to that the traditional algorithms do.It has been applied to the simulated data array decomposition andobtained reasonable results.It showed that NMF3 could be introduced for curve resolution in chemometrics. 相似文献