三角晶场中4A2(3d3)态离子全组态EPR理论研究

在中间场耦合图像中,建立了4A2(3d3)态离子全组态EPR理论;研究了EPR参量随三角晶场参量V、V′及立方晶场参量Dq变化关系;用完全对角化方法验证了MacfarlaneEPR参量的三阶微扰公式,结果表明,在较大的晶场范围内微扰公式的收敛性很好;研究了EPR参量的微观起源及自旋二重态对EPR参量的贡献,指出自旋二重态对零场分裂参量的贡献不可忽略,二重态对g因子的贡献甚微.     

全透射近红外光谱的苹果整果糖度在线检测模型优化

光谱质量、样本个体差异、检测系统和建模算法等多种因素共同决定水果糖度检测模型的预测精度和稳定性。采用自主研发的短积分全透射近红外在线检测系统以5 ms积分时间和0.5 m·s-1运行速度在线获取了“富士”苹果全透射光谱信号。不同姿态获取的透射光谱强度差异明显,但曲线走势相近,均在920 nm波段具有最大的光谱强度,在850 nm波段存在波谷。采用移动平均平滑、标准正态变量变换和多元散射校正等预处理方法有效去除原始光谱的随机噪声和基线偏差,减小了样本检测姿态引起的光谱差异。为分析不同检测姿态对苹果整果糖度预测模型的影响,构建了单一姿态局限模型和多姿态通用模型,结果表明基于全位点平均透射光谱构建的单一姿态局限模型对检测姿态具有很大的局限性,而多姿态通用模型预测能力较单一检测姿态相当,但却对不同的检测姿态具有更强的适用能力。为进一步提高光谱信号质量,优化模型预测能力,采用信号强度阈值优选方法实现了苹果整果糖度预测模型优化,发现移除中央位点获取的透射光谱信号,有利于提高苹果整果糖度预测模型精度。多姿态通用信号强度优化模型综合考虑不同姿态获取的光谱信息有效性,有效提升了通用信号强度优化模型的预测能力和稳定性,当多姿态通用模型中信号强度阈值为5 000时,模型预测性能最佳,其预测参数R_p,RMSEP和RPD分别为0.79,0.84%和1.58。表明短积分全透射近红外在线检测系统用于不同姿态苹果糖度预测是可行的,多姿态通用模型的建立,扩大了模型在不同姿态的预测稳健性,短积分光谱采集方式结合信号强度阈值优选方法提升了光谱信号的质量和模型的预测能力。     

Parallel application of block-iterative methods in medical imaging and radiation therapy

Some row-action algorithms which exploit special objective function and constraints structure have proven advantageous for solving huge and sparse feasibility or optimization problems. Recently developed block-iterative versions of such special-purpose methods enable parallel computation when the underlying problem is appropriately decomposed. This opens the door for parallel computation in image reconstruction problems of computerized tomography and in the inverse problem of radiation therapy treatment planning, all in their fully discretized modelling approach. Since there is more than one way of deriving block-iterative versions of any row-action method, the choice has to be made with reference to the underlying real-world problem.This research was done with partial support of National Institutes of Health, Grant HL-28438 while the author was with the Medical Image Processing Group (MIPG) at the Department of Radiology, Hospital of the University of Pennsylvania, Philadelphia, PA, USA.     

基于等离激元热电子调控的全谱光催化产氢增强（英文）

等离激元效应在光催化体系中的集成为实现广谱光吸收提供了一个新的途径,然而等离激元热电子的较低迁移率和不确定扩散方向使得其光催化效率仍较低.等离激元金属与n型半导体接触后,其界面间会形成肖特基结.在特定波长太阳光照射下,等离激元金属将其表面等离子体能量聚集在表面自由电子上,进而产生热电子.当这些热电子具有的能量高于肖特基势垒时,热电子便可注入到半导体导带上.与此同时,半导体上的电子可以通过肖特基接触发生回流,与金属上的空穴复合,进而降低半导体-等离激元金属复合材料的光催化性能.因此,为了提高光催化效率,如何调控等离激元热电子迁移和充分利用等离激元效应是一个重要挑战.本文尝试将"表面异质结"与肖特基结相结合的复合结构,得以有效地调控等离激元热电子的迁移.在该复合结构中,金纳米颗粒和铂纳米颗粒分别作为等离激元吸光单元和助催化剂,集成在TiO_2纳米片表面.其中"表面异质结"是由TiO_2纳米片的两种不同表面晶面所构成,我们选择由{001}和{101}两组晶面组成的TiO_2纳米片作为半导体衬底.该结构中的{001}晶面导带能级高于{101}导带能级,因而电子由高能级的{001}流向低能级的{101}晶面,可以用来引导等离激元热电子从可见光响应的金纳米颗粒向TiO_2进行高效转移.通过巯基丙酸的桥联作用,将等离激元Au纳米颗粒锚定在TiO_2纳米片的{001}晶面上,获得Au-TiO_2{001}样品.另一方面,利用TiO_2纳米片自身光生电荷导向性光沉积,得到与{101}晶面结合形成的Au-TiO_2{101}样品.我们对两组样品进行光电流和光催化产氢实验对比,确认在"表面异质结"诱导下Au-TiO_2{001}样品中Au产生的光生热电子可以更好地注入到TiO_2纳米片导带上.我们进一步通过光沉积Pt纳米颗粒来判定光生电子所能到达的区域,验证了以上结论.与此同时,肖特基结由铂纳米颗粒与TiO_2纳米片所形成,可以促使电子由TiO_2向铂纳米颗粒进行转移,而避免发生向金纳米颗粒的反向迁移,从而在Au-TiO_2体系中实现高效的单向载流子转移.基于该设计,等离激元光催化剂实现了明显改善的全谱光催化产氢性能.本文为全谱光催化的复合结构理性设计提供了一个新的思路.     

A full information pricing problem for the sale of several identical commodities

Summary k commodities of the same kind are for sale in a finite time intervalI, and potential customers arrive according to a Poisson process. It is assumed that no customer may buy more than one unit. The seller has to fix, for eacht I, a price for which he is willing to sell a commodity at timet. This decision is based on the knowledge of the probabilities that a customer appearing at timet will accept a price of at mostx monetary units (for allt I andx > 0). There is no possibility of recall of previous customers. We characterize an optimal price function and the maximal expected gain. Further the relation to the persistency problem of Elfving (1967) is exhibited.

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Zusammenfassung k gleichartige Güter sollen in einem endlichen ZeitintervallI an Kunden verkauft werden, deren Ankunftszeitpunkte einen Poisson-Prozeß bilden. Es wird angenommen, daß kein Kunde mehr als eine Einheit kauft. Der Verkäufer muß für jedest I einen Preis angeben, zu dem er eine Einheit zum Zeitpunktt im Falle einer Nachfrage verkaufen würde. Es wird vorausgesetzt, daß er für jedest I und jedesx>0 die Wahrscheinlichkeit kennt, daß ein zur Zeitt eintreffender Kunde höchstens den Preisx für das Gut akzeptiert; die Möglichkeit, auf frühere Kunden zurückzugreifen, ist ausgeschlossen. Für diese Situation wird eine optimale Preisfunktion sowie der zugehörige maximale erwartete Erlös bestimmt. Ferner wird die Beziehung dieses Modells zu einem verwandten Problem von Elfving (1967) herausgestellt.

     

Optimal group symmetric localized molecular orbitals

Summary The concept and generating method of optimum group symmetric localized molecular orbitals (OSLMOs) are proposed. The OSLMOs have strong points of orthogonality, equivalence and symmetry, and they are simultaneously as close to the classical VB structure as possible. By using the OSLMOs as one-electron orbitals the multiconfigurational correlation calculations are reduced. The scheme is also a valuable popularization and development to hybridization theory.     

Stationary perturbation theory

Summary After a short recapitulation of the basic concepts of stationary perturbation theory, this is applied to a many-electron Hamiltonian, with or without an external field, given in a Fock space formulation in terms of a finite basis, the exact eigenfunctions of which are the full-CI wave functions. The Lie algebra _c ⁿ of the variational group corresponding to this problem is presented. It has an important subalgebra _c ⁽¹⁾ of one-particle transformations. Hartree-Fock and coupled Hartree-Fock (also uncoupled Hartree-Fock) as well as MC-SCF and coupled MC-SCF are outlined in this framework. Many-body perturbation theory and Møller-Plesset perturbation theory are derived from the same kind of stationarity condition and a new non-perturbative iteration construction of the full-CI wave function is proposed, the first Newton-Raphson iteration cycle of which is CEPA-0. For the treatment of electron correlation for properties two variants of Møller-Plesset theory referred to as coupled (CMP) and uncoupled (UCMP) are defined, neither of which is fully satisfactory. While CMP satisfies a Brillouin condition, which implies that first order correlation corrections to first- and second-order properties vanish, it does not satisfy a Hellmann-Feynman theorem, i.e. a first order property isnot the expectation value of the operator associated with the property. Conversely UCMP satisfies a Hellmann-Feynman theorem but no Brillouin theorem. The incompatibility of the two theorems is related to an unbalanced treatment of one-particle- and higher excitations in MP theory. CMP, which is based on coupled Hartree-Fock as uncorrelated reference, appears to have slight advantages over UCMP, but neither variant looks very promising for the evaluation of 2nd order correlation corrections to 2nd-order properties. Then four variants of the perturbation theory of properties with a nonperturbative treatment of electron correlation on CEPA-0 level (but extendable to a higher level) are discussed. While those variants which are the direct counterpart of UCMP and CMP must be discarded, the perturbative CEPA-0 derived from a perturbative treatment on full-CI level appears to satisfy all important criteria, in particular it satisfies a Brillouin-Brueckner condition and a Hellmann-Feynman theorem. A simplified version, the coupled Brillouin-Brueckner CEPA-0 appears to have essentially the same qualities. It is important to replace the Brillouin condition of MP theory by the Brillouin-Brueckner condition in non-perturbative approaches, especially if one is interested in properties.     

Full-wave analysis of stripping chronopotentiograms at scanned deposition potential (SSCP) as a tool for heavy metal speciation: Theoretical development and application to Cd(II)-phthalate and Cd(II)-iodide systems

A new mathematical treatment has been developed and implemented in an EXCEL spreadsheet in order to determine average equilibrium functions from the full set of data measured by scanning stripping chronopotentiometry (SSCP) in solutions containing different proportions of heavy metal ions and small-sized ligands. It has been applied to the experimental systems Cd(II)-phthalate and Cd(II)-iodide as models of complexation in the absence and in the presence of electrodic adsorption, respectively. The good agreement between the complexation parameters determined in this way, those predicted from literature data and those obtained using a cadmium ion selective electrode (ISE) confirms the validity of the proposed methodology and encourages its further refining for the analysis of macromolecular and heterogeneous systems.     

The three-dimension model for the rock-breaking mechanism of disc cutter and analysis of rock-breaking forces

To study the rock deformation with threedimensional model under rolling forces of disc cutter,by carrying out the circular-grooving test with disc cutter rollingaround on the rock,the rock mechanical behavior underrolling disc cutter is studied,the mechanical model of disccutter rolling around the groove is established,and the theory of single-point and double-angle variables is proposed.Based on this theory,the physics equations and geometricequations of rock mechanical behavior under disc cutters oftunnel boring machine(TBM) are studied,and then the balance equations of interactive forces between disc cutter androck are established.Accordingly,formulas about normalforce,rolling force and side force of a disc cutter are derived,and their validity is studied by tests.Therefore,a newmethod and theory is proposed to study rock-breaking mechanism of disc cutters.