排名聚合算法在少量长列表聚合中的性能比较分析

排名聚合将多个排名列表聚合成一个综合排名列表,可应用于推荐系统、链路预测、元搜索、提案评选等.当前已有工作从不同角度对不同排名聚合算法进行了综述、比较,但存在算法种类较少、数据统计特性不清晰、评价指标不够合理等局限性.不同排名聚合算法在提出时均声称优于已有算法,但是用于比较的方法不同,测试的数据不同,应用的场景不同,因此何种算法最能适应某一任务在很多情况下仍不甚清楚.本文基于Mallows模型,提出一套生成统计特性可控的不同类型的排名列表的算法,使用一个可应用于不同类型排名列表的通用评价指标,介绍9种排名聚合算法以及它们在聚合少量长列表时的表现.结果发现启发式方法虽然简单,但是在排名列表相似度较高、列表相对简单的情况下,能够接近甚至超过一些优化类方法的结果;列表中平局数量的增长会降低聚合排名的一致性并增加波动;列表数量的增加对聚合效果的影响呈现非单调性.整体而言,基于距离优化的分支定界方法 (FAST)优于其他各类算法,在不同类型的排名列表中表现非常稳定,能够很好地完成少量长列表的排名聚合.     

Spectrochemical Properties of Noncubical Transition Metal Complexes in Solutions. XIV. Angular Overlap Studies of bis(Salicylidene-2-aminothiazole)Copper(II) in Various Solvents

The copper(II) complex [Cu(sat)], where Hsat is salicylidene-2-aminothiazole (bidentate Schiff - base), was studied in variety of solvents. In the solid state, the complex is black. It has been characterized by elemental analysis, solubility in common solvents, molar conductivity, and ultraviolet (UV) and visible (Vis) spectroscopy. The complex is easily soluble in common solvents such as chloroform, dimethylformamide, dimethyl sulfoxide, and 1,4-dioxane. The known crystal structure of similar compounds shows planar coordination geometry for the copper center. Combined multitechnique experiments have been applied to confirm the structure of the complex in solutions. The molar conductivities indicate their nonelectrolyte properties in all these solvents. The spectroscopic measurements were used to study the coordination properties of donoratoms and their bonding abilities.     

毛细管电色谱中双电层叠加的研究

通过流动相中电解质浓度对毛细管电色谱柱效能的流动相平均线速度的影响，研究了ＣＥＣ中双电层叠加现象。提出选择合适电解质组成的浓度及在制备色谱柱过程中避免细小和破碎的固定相颗粒进入柱中，以有效地减小双电层叠加作用。     

Multipole expansion of diatomic overlap

A systematic extension of Ruedenberg's expansion formula is applied to evaluate two-electron integrals occurring in calculations on molecular structure. Minimum STO basis sets are used for all SCF-calculations within the framework of the MEDO-method (Multipole Expansion of Diatomic Overlap). The errors due to this approximation scheme are almost negligible compared to those introduced by the truncated basis set: LiH, Li₂ and N₂ are chosen as examples.     

Optimization of auxiliary basis sets for the LEDO expansion and a projection technique for LEDO-DFT

We present a systematic procedure for the optimization of the expansion basis for the limited expansion of diatomic overlap density functional theory (LEDO-DFT) and report on optimized auxiliary orbitals for the Ahlrichs split valence plus polarization basis set (SVP) for the elements H, Li--F, and Na--Cl. A new method to deal with near-linear dependences in the LEDO expansion basis is introduced, which greatly reduces the computational effort of LEDO-DFT calculations. Numerical results for a test set of small molecules demonstrate the accuracy of electronic energies, structural parameters, dipole moments, and harmonic frequencies. For larger molecular systems the numerical errors introduced by the LEDO approximation can lead to an uncontrollable behavior of the self-consistent field (SCF) process. A projection technique suggested by L?wdin is presented in the framework of LEDO-DFT, which guarantees for SCF convergence. Numerical results on some critical test molecules suggest the general applicability of the auxiliary orbitals presented in combination with this projection technique. Timing results indicate that LEDO-DFT is competitive with conventional density fitting methods.     

Statistical-overlap theory for elliptical zones of high aspect ratio in comprehensive two-dimensional separations

The low prediction by statistical-overlap theory of the numbers of singlets and peaks in two-dimensional separations containing zones represented by either circles of small number or eccentric ellipses of any number is shown to result from use of probability expressions for unbound spaces of infinite extent. An exact theory is derived for the probability of singlet formation in a reduced two-dimensional space of unit length, width, and area. The probability is a weighted sum of the probabilities of singlet formation in the interior, edge, and corner regions of the space, which depend only on saturation. The weighting factors are the fractions of area associated with each region and depend on the number of zones, the aspect ratio, the saturation, and the ellipse's spatial orientation. The average numbers of doublets, triplets, and peaks in the space are approximated by combining these results with Roach's equations describing the clustering of circles in an unbound two-dimensional space. Simulations show that theory predicts the number of singlets, doublets, triplets, and peaks, when the number of zones is 25 or more, the aspect ratio is 100 or less, and the saturation is 2 or less. The relationship is derived between the aspect ratios of ellipses in the reduced space and actual separation space. Calculations are presented for comprehensive two-dimensional gas chromatography.     

The role of the π-bonding network for trigonal level splittings of tris-bidentate Cr(acac)3 and Cr(ox) 3 3−

The varying -bonding contributions in the title compounds caused by the different electronic and molecular structure of the chelate rings are used for explaining the large band splittings in the absorption spectra by trigonal symmetry. It is shown that usual ligand field theory and the angular overlap model are not able to account for the trigonal level splitting of Cr(acac)₃ for which the coordination sphere of oxygen atoms is nearly octahedrally arranged. The experimental finding can, however, be rationalized by an extended angular overlap model which considers the phase coupling of -orbitals in the ligands leading to non-additive contributions to the metal-ligand bond energy.On leave of absence from the Bulgarian Academy of Sciences, Sofia, Bulgaria     

Simple correction for perturbations of peak amplitudes in statistical models of overlap

Summary The application of statistical models of overlap (SMOs) to saturated separations is made possible by theory that addresses variable peak amplitudes. These amplitudes cause peak widths to vary, and this variation can be modeled by a random variable whose effect on the probability of overlap is expressed by a convolution integral. Modified probabilities of overlap are derived for both homogeneous and nonhomogeneous one-dimensional separations, and the new probabilities are compared to results determined from published computer simulations. The new theory can describe overlap at saturations that are 3 to 4 times larger than before. Previously reported experimental chromatograms are reinterpreted to show the capabilities of theory. The theoretical extension is an important step towards making SMOs into practical tools for screening analytical separations.     

支化高分子在溶液中的交叠与缠结

溶液中高分子的交叠和缠结与其链结构密切相关。支化聚苯乙烯的临界交叠浓度C和临界缠结浓度C_E比分子量相同的线型聚苯乙烯的大,说明交叠和缠结同分子在溶液中线团的体积有直接关系。     

Spectrochemical Properties of Noncubical Transition Metal Complexes in Solutions. IX. The Mixed Tetragonal Distorted Bis(Salicylato)Cobalt(II) Complex in Various Solvents

Mixed cobalt(II) complexes with the monodentate ligands: 2-hydroxybenzoic acid deprotonated (sal^–, the salicylate ion) and water, have been investigated. The combined results of the spectrophotometric and conductance measurements, as well as known the X-ray structure for solids, were used to determine the structure of the studied complexes in solution. The electronic absorption spectra in aqueous acid (0.01M HClO₄), ethylene glycol (glycol), formamide (FM), N,N-dimethylformamide (DMF), and dimethyl sulfoxide (DMSO) solutions have been recorded. The d-d electronic spectra have been treated by the crystal-field model (CFM) and angular overlap model (AOM). Low-symmetry splittings of the broad asymmetric bands in the experimental spectra (solutions at room temperature) were found by Gaussian analysis. The effect of the and bonding of the monodentate ligands (with oxygen-donor ligators) on the central metal ion was described in the ligand–field framework. A comparison of the stereochemistry of the complex species in various solutions was made.