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11.
This paper investigates regression quantiles (RQ) for unstable autoregressive models. The uniform Bahadur representation of the RQ process is obtained. The joint asymptotic distribution of the RQ process is derived in a unified manner for all types of characteristic roots on or outside the unit circle. It involves stochastic integrals in terms of a sequence of independent and identically distributed multivariate Brownian motions with correlated components. The related L-estimator is also discussed. The asymptotic distributions of the RQ and the L-estimator corresponding to the nonstationary componentwise arguments can be transformed into a function of a normal random variable and a sequence of i.i.d. univariate Brownian motions. This is different from the analysis based on the LSE in the literature. As an auxiliary theorem, a weak convergence of a randomly weighted residual empirical process to the stochastic integral of a Kiefer process is established. The results obtained in this paper provide an asymptotic theory for nonstationary time series processes, which can be used to construct robust unit root tests. 相似文献
12.
该文用顺磁离子对其近邻~(13)C核的NMR吸收增宽效应,系统地研究了抗坏血酸在不同溶剂中对金属离子Mn~(2+)、Gd~(3+)的配合行为.在水溶液中,抗坏血酸可通过两种配合方式与Mn~(2+)作用,但与Gd~(3+)的作用只有一种稳定的结构.在水中抗坏血酸对金属的配位活性部位分别是1位羟基氧,3位离解的羟基氧和6位羟基氧.在DMSO中,3位羟基由于H~+对该基团的静电遮蔽而变得对金属离子Mn~(2+)表现为配位惰性,同时6位羟基配位活性较大增强.对Gd~(3+)来说,此时没有优势配位活性部位存在.文章还讨论了抗坏血酸在H_2O-DMSO混合溶剂中的~(13)C NMR谱及在DMSO中NaOH对其~(13)C NMR谱及其与金属络合结构的影响. 相似文献
13.
J.-L. Garden 《Thermochimica Acta》2007,452(2):85-105
What is really measured in dynamic calorimetric experiments is still an open question. This paper is devoted to this question, which can be usefully envisaged by means of macroscopic non-equilibrium thermodynamics. From the pioneer work of De Donder on chemical reactions and with other authors along the 20th century, the question is tackled under an historical point of view. A special attention is paid about the notions of frequency dependent complex heat capacity and entropy production due to irreversible processes occurring during an experiment. This phenomenological approach based on thermodynamics, not widely spread in the literature of calorimetry, could open significant perspectives on the study of macro-systems undergoing physico-chemical transformations probed by dynamic calorimetry. 相似文献
14.
Manicka Dhanasekar Jianjun Han Qinghua Qin 《Finite Elements in Analysis and Design》2006,42(14-15):1314-1323
Much work on special elements that simplify geometrical modelling of structures containing holes, cracks and/ or inclusions has been reported extensively in the literature. This paper presents a hybrid-Trefftz element containing elliptic hole formulated using Hellinger–Reissner principle by employing trial functions based on the mapping technique and the Cauchy integral method. The element presented in this paper could be regarded as an improved formulation over Piltner [Special finite elements with holes and internal cracks, Int. J. Numer. Methods Eng. 21 (1985) 1471–1485] element because the chosen trail functions in this paper have provided relatively more stable solutions. The use of the element with other ordinary displacement-based finite elements has also yielded very accurate solutions even when very coarse meshes relative to the size of the elliptic hole have been used. 相似文献
15.
J. A. M. Janssen 《Journal of statistical physics》1989,57(1-2):187-198
The master equation for a complex chemical reaction cannot always be reduced to a simpler master equation, even if there are fast and slow individual reaction steps. Nevertheless the elimination of intermediates can be carried out with the help of the-expansion. This is illustrated with a well-known complex reaction: the dissociation of N2O5. It is shown that the intrinsic fluctuations in the N2O5 decay are larger than those implied by the master equation suggested by the macroscopic rate law. 相似文献
16.
双邻苯二酚锑二甲基羟乙铵的晶体结构 总被引:3,自引:1,他引:3
含锑配合物是治疗血吸虫病、肿瘤等的常用药物,我们曾对双邻苯二酚锑二乙基羟乙胺进行了晶体结构测定,本文简要报导双邻苯二酚锑二甲基羟乙胺的结构.锑化合物的制法与其二乙基羟乙铵衍生物类似.产物为淡黄色晶体,它在水溶液中长时间放置会变成紫黑色,因此,制得的晶体须立即用丙酮溶解进行重结晶.晶体的密度为1.667g/cm~3.按C_(16)H_(20)O_5NSb的元素分析结果(%)如下:Sb 28.3(28.5),C 43.9(44.9),N 3.3(3.3),H 4.7(4.7).括号内为理论值. 相似文献
17.
络合吸附体系吸附性的研究 总被引:3,自引:0,他引:3
本文论述了研究络合吸附体系吸附性的重要意义,较详细地讨论了各种方法,包括微分电容曲线法、交流极谱法和计时电量法等在吸附性研究和吸附量测定中的应用。 相似文献
18.
首次合成了喹喔啉-2,3-二甲酰胺(Qxda)与3d过渡金属的三种固体配合物:M(Qxda)2cl2(M=Co(I),Ni(I),Cu(Ⅱ)。通过元素分析,摩尔电导,红外光谱,电子光谱,磁化率,热分析等手段对配合物的组成和性质进行了研究。 相似文献
19.
David W. Schwenke 《Theoretical chemistry accounts》1988,74(5):381-402
A new method for the direct calculation of resonance parameters is presented. It is based upon searching for poles of the scattering matrix at complex energies. This search is expedited by the use of analytic derivatives of the scattering matrix with respect to the total energy. This procedure is applied initially to a single channel problem, but is generalizable to more complicated systems. Using the most accurate available potential energy data, we calculate resonance parameters for all of the physically important quasibound states of the ground electronic state of the hydrogen molecule. Corrections to the Born-Oppenheimer potential are included and assessed. The new method has no difficulty locating resonances with widths greater than about 1×10–7 cm–1. It is easier to find narrow resonances by monitoring the dependence of the imaginary part of the reactance matrix on the real part of a complex energy than to monitor the dependence of the eigenphase sum on energy at real energies. 相似文献
20.
多氮杂大环与许多金属离子能形成稳定的络合物。由于氮原子是三价的,因而多氮杂大环比冠醚具有更有利的结构;如果再导入羧基、膦酸基以及其他的亲水基团,则可得到一系列能形成水溶性金属络合物的配体。其中某些金属(如铜、钇等)的络合物在人体生理条件下表现出很好的稳定性,结合单原抗体技术的应用,这炎络合物在医疗、诊断方面有实用性。本文简单介绍某些代表性络合物的制备方法、物理性能和可能的应用。 相似文献