SiN团簇光电子能谱的指认

应用含时密度泛函理论研究了SiN团簇低能激发态的性质.将计算结果与前人已有的计算结果进行了比较，此外还根据计算得到的低能激发能对SiN^-阴离子的光电子能谱进行了理论指认.研究表明，SiN^-阴离子的基态为¹Σ态，而光电子能谱上的X峰和A峰分别对应于¹Σ→²Σ和¹Σ→²Π的跃迁.研究结果还表明，用含时密度泛函的方法来处理激发态的问题是成功的. 关键词： 团簇 光电子能谱 基态 激发态     

High pressure X-ray diffraction study of CdAl2Se4 and Raman study of AAl2Se4 (A=Hg, Zn) and CdAl2X4 (X=Se, S)

We report the results of an X-ray diffraction study of CdAl₂Se₄ and of Raman studies of HgAl₂Se₄ and ZnAl₂Se₄ at room temperature, and of CdAl₂S₄ and CdAl₂Se₄ at 80 K at high pressure. The ambient pressure phase of CdAl₂Se₄ is stable up to a pressure of 9.1 GPa above which a phase transition to a disordered rock salt phase is observed. A fit of the volume pressure data to a Birch-Murnaghan type equation of state yields a bulk modulus of 52.1 GPa. The relative volume change at the phase transition at ∼9 GPa is about 10%. The analysis of the Raman data of HgAl₂Se₄ and ZnAl₂Se₄ reveals a general trend observed for different defect chalcopyrite materials. The line widths of the Raman peaks change at intermediate pressures between 4 and 6 GPa as an indication of the pressure induced two stage order-disorder transition observed in these materials. In addition, we include results of a low temperature Raman study of CdAl₂S₄ and CdAl₂Se₄, which shows a very weak temperature dependence of the Raman-active phonon modes.     

Structural and electronic properties of graphite layers grown on SiC(0 0 0 1)

Photoelectron spectroscopy, low-energy electron diffraction, and scanning probe microscopy were used to investigate the electronic and structural properties of graphite layers grown by solid state graphitization of SiC(0 0 0 1) surfaces. The process leads to well-ordered graphite layers which are rotated against the substrate lattice by 30°. On on-axis 6H-SiC(0 0 0 1) substrates we observe graphitic layers with up to several 100 nm wide terraces. ARUPS spectra of the graphite layers grown on on-axis 6H-SiC(0 0 0 1) surfaces are indicative of a well-developed band structure. For the graphite/n-type 6H-SiC(0 0 0 1) layer system we observe a Schottky barrier height of ?_B,n = 0.3 ± 0.1 eV. ARUPS spectra of graphite layers grown on 8° off-axis oriented 4H-SiC(0 0 0 1) show unique replicas which are explained by a carpet-like growth mode combined with a step bunching of the substrate.     

Large set of P3‐decompositions

Let G=(V(G),E(G)) be a graph. A (n,G, λ)‐GD is a partition of the edges of λK_n into subgraphs (G‐blocks), each of which is isomorphic to G. The (n,G,λ)‐GD is named as graph design for G or G‐decomposition. The large set of (n,G,λ)‐GD is denoted by (n,G,λ)‐LGD. In this work, we obtain the existence spectrum of (n,P₃,λ)‐LGD. © 2002 Wiley Periodicals, Inc. J Combin Designs 10: 151–159, 2002; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/jcd.10008     

复合体系方法测量液体力学谱

本文介绍了采用复合体系，测量得到凝聚态物质从固态到液态连续变化力学谱的一种新的实验方法。以簧振动为例，给出了解析的计算公式，以及应用条件。通过进一步综合分析，得到具有更广应用范围的近似公式，可以近似应用于其他不同的振动模式，如低频扭摆。应用新的测量方法，给出了典型小分子玻璃材料甘油和碳酸丙稀从玻璃态到液态的力学谱，观察到甘油和碳酸丙稀玻璃化转变、碳酸丙稀的再结晶、熔化和挥发的过程；测量得到挥发过程中水的质量随时间精确变化的曲线。最后，本文给出了新方法的一些应用展望。     

Simple, expedient methods for the determination of water and electrolyte contents of cellulose solvent systems

The concentrations of water, W, and electrolytes present in solutions of LiCl in N,N-dimethylacetamide, LiCl/DMAc, and of tetrabutylammonium fluoride. x-hydrate in DMSO, TBAF.xW/DMSO can be accurately and expediently determined by three independent methods, UV–vis, FTIR and EMF measurement. The first relies on the use of solvatochromic probes whose spectra are sensitive to solution composition. It is applicable to W/LiCl/DMAc solutions but not to TBAF.xW/DMSO, because the charge-transfer complex bands of the probes are suppressed by strong interactions with the latter electrolyte. Integration of ν_OH band of water may be employed in order to determine [W], hence [electrolyte] by weight difference. EMF measurement uses ion-selective electrodes in order to determine [electrolyte], hence [W] by weight difference. Results of the latter method were in excellent agreement with those of FTIR. The reason for the failure of Karl Fischer titration is addressed, and the relevance of the results obtained to functionalization of cellulose under homogenous solution conditions is briefly commented on.     

Modification of the surface state of rough substrates by two different varnishes and influence on the reflected light

Modification of the visual appearance when a rough surface is covered by a varnish is mostly attributed to the levelling of the substrate surface, which depends on the molecular weight of the varnish. The topography of varnished surfaces, however, has never been measured directly. Surfaces of varnishes applied over glass substrates of varying roughness were studied, therefore, using mechanical profilometry. Two different varnishes made with a low and a high molecular weight resin were studied. Both varnishes lower the r.m.s. roughness of the substrates and filter the high spatial frequencies. These results are amplified for the varnish containing the low molecular weight resin. The light reflected by the varnished samples is modelled from these topographical data. Its angular distribution, calculated from the probability density of slopes is presented, taking into account separately the air/varnish and the varnish/substrate interfaces. These analyses are presented in a back-scattering configuration. They show that varnishing significantly reduces the angular width of the reflected light and that this effect is magnified for the low molecular weight resin. Modelling furthermore shows that the influence of the roughness of the varnish/substrate interface is negligible in the total reflected light.     

Formation and hydrogenation of p(2 × 2)-N on Pt(1 1 1)

The formation of a well-ordered p(2 × 2) overlayer of atomic nitrogen on the Pt(1 1 1) surface and its reaction with hydrogen were characterized with reflection absorption infrared spectroscopy (RAIRS), temperature programmed desorption (TPD), low energy electron diffraction (LEED), Auger electron spectroscopy (AES), and X-ray photoelectron spectroscopy (XPS). The p(2 × 2)-N overlayer is formed by exposure of ammonia to a surface at 85 K that is covered with 0.44 monolayer (ML) of molecular oxygen and then heating to 400 K. The reaction between ammonia and oxygen produces water, which desorbs below 400 K. The only desorption product observed above 400 K is molecular nitrogen, which has a peak desorption temperature of 453 K. The absence of oxygen after the 400 K anneal is confirmed with AES. Although atomic nitrogen can also be produced on the surface through the reaction of ammonia with an atomic, rather than molecular, oxygen overlayer at a saturation coverage of 0.25 ML, the yield of surface nitrogen is significantly less, as indicated by the N₂ TPD peak area. Atomic nitrogen readily reacts with hydrogen to produce the NH species, which is characterized with RAIRS by an intense and narrow (FWHM ∼ 4 cm⁻¹) peak at 3322 cm⁻¹. The areas of the H₂ TPD peak associated with NH dissociation and the XPS N 1s peak associated with the NH species indicate that not all of the surface N atoms can be converted to NH by the methods used here.     

A dynamical test of phase transition order: New things in old places or old wine in new bottles

We first discuss nonlinear aspects of phase transition theory applied to a particular liquid crystal phase transition. A simple derivation is given to show how two coupled Goldstone modes (one appearing as gauge fluctuations of the ordered phase) can force a phase transition, against all expectations, to take place discontinuously (theory of Halperin, Lubensky, and Ma)-but the discontinuity may be immeasurably small. Then, we describe a new dynamical test of phase transition order, developed by Cladiset al., that turns out to be more sensitive than x-ray diffraction and adiabatic calorimetry. Quantitative data found by this new method are in excellent agreement with the measurements of adiabatic calorimetry and x-ray diffraction as well as expectations implicit in the predictions of HLM.This is the text of an after-banquet talk given at the CNLS Workshop on the Dynamics of Concentrated Systems.