A detailed analysis of the photoemission spectra of basic thioaromatic monolayers on noble metal substrates

Analysis of photoemission spectra of complex thioaromatic self-assembled monolayers (SAMs) requires the knowledge and understanding of such spectra for the basic systems. Keeping this goal in mind, synchrotron-based high-resolution X-ray photoelectron spectroscopy was used to characterize SAMs formed from the simplest thioaromatic compounds, namely thiophenol, 1,1′-biphenyl-4-thiol and 1,1′;4′,1″-terphenyl-4-thiol on evaporated Au(1 1 1) and Ag(1 1 1) substrates. The acquired S 2p and C 1s spectra were analyzed in terms of fine structure and initial and final state effects in the photoemission process. The assignment of the individual spectral features was considered in detail. Conclusions on quality and chemical and structural homogeneity of the investigated SAMs were derived.     

Investigation of chemical decomposition of CCl4 on TiO2 near room temperature

Dissociative adsorption of CCl₄ on TiO₂ at 35 °C has been studied by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and electron spin resonance. CCl₄ decompose to form CO, CO₂, and CO₃ on the surface, at such a low temperature, in which CO₂ formation is not from CO oxidation on TiO₂, but CO₃ can be produced by CO and CO₂ adsorption. The Cl generated from CCl₄ decomposition is left on the surface and bonded to titanium ions. Mineralization of CCl₄ on TiO₂ involves the lattice oxygens. Thermodynamical driving force and possible reaction routes for CO and CO₂ formation in the CCl₄ decomposition on TiO₂ are discussed.     

Surface morphologies of anthracene single crystals grown from vapor phase

The morphologies and lattice structures of anthracene single crystals grown from the vapor phase were investigated using optical microscopy, phase contrast microscopy, atomic force microscopy (AFM), and X-ray diffraction analysis. Common morphologies with hexagonal large planes were observed irrespective of crystal size. The observation of certain surface morphologies with a phase contrast microscopy revealed that the spiral steps originated from screw dislocations present on the (0 0 1) planes. Moreover, the center and edge of the (0 0 1) planes had large curvatures, similar to hills. Resultantly, quarter-monolayer (ML) steps were observed on the large and flat planes between both hills.     

喷气式Z箍缩等离子体辐射软X射线能谱的研究

研制了一台五通道ROSS-FILTER-PIN软X射线能谱仪，能谱范围为0.28—1.56keV.它由5个连续能段组成，每个能段的起止边由罗斯滤片对(ROSS-FILTERS)的L或K吸收边确定.罗斯滤片对的厚度通过优化计算得到，为了使每个通道的灵敏区外响应(即所测能段外响应)与通道总响应之比最小，在滤片对的第二滤片上镀上了一定厚度的第一滤片材料；为了缩减滤片表面积以增强低能滤片的抗冲击能力及方便滤片加工，能谱仪采用了小探测面积的PIN探测器(1mm²).借助此能谱仪，测量得到了喷气式Z箍缩(Z-pinch)等离子体辐射软X射线能谱的分布，并研究了软X射线产额随箍缩状况的变化趋势. 关键词： Z箍缩等离子体 罗斯滤片 软X射线能谱     

Exact Max-SAT solvers for over-constrained problems

We present a new generic problem solving approach for over-constrained problems based on Max-SAT. We first define a Boolean clausal form formalism, called soft CNF formulas, that deals with blocks of clauses instead of individual clauses, and that allows one to declare each block either as hard (i.e., must be satisfied by any solution) or soft (i.e., can be violated by some solution). We then present two Max-SAT solvers that find a truth assignment that satisfies all the hard blocks of clauses and the maximum number of soft blocks of clauses. Our solvers are branch and bound algorithms equipped with original lazy data structures, powerful inference techniques, good quality lower bounds, and original variable selection heuristics. Finally, we report an experimental investigation on a representative sample of instances (random 2-SAT, Max-CSP, graph coloring, pigeon hole and quasigroup completion) which provides experimental evidence that our approach is very competitive compared with the state-of-the-art approaches developed in the CSP and SAT communities. Research partially supported by projects TIN2004-07933-C03-03 and TIC2003-00950 funded by the Ministerio de Educación y Ciencia. The second author is supported by a grant Ramón y Cajal.     

Growth and characterization of model oxide catalysts

Oxide catalysts are frequently used to convert toxic species to environmentally benign molecules, and to prevent the formation of toxic species in the first place. In this paper, growth and characterization of model oxide systems employed in both approaches is discussed. An example of the former approach is the selective catalytic reduction (SCR) of NO emitted from power plants by NH₃, which employs tungsten and vanadium oxides supported on the anatase polymorph of TiO₂. To model SCR catalysts, epitaxial titanium, vanadium and tungsten oxide films were grown using molecular beam epitaxy and magnetron sputtering. Two different anatase orientations were grown on LaAlO₃ substrates and their interactions with vanadia were characterized. On LaAlO₃ (0 0 1), anatase exposed a (4 × 1) reconstructed (0 0 1) surface. Vanadia lifted the reconstruction and at 1 ML a (1 × 1) surface with mostly V⁵⁺ was observed. Continued V₂O₅ growth led to loss of order, but at high temperatures epitaxial VO₂ could be grown; vanadia behaved similarly on anatase films on LaAlO₃ (1 1 0). Results suggested that the monolayer is pseudomorphic with O adsorption oxidizing the surface V to 5+, since the anatase structure cannot accommodate more bulk oxygen, only a monolayer can be pseudomorphic and have only V⁵⁺. Thus the vanadia monolayer has unique structural and chemical properties that can help explain why vanadia monolayers on TiO₂ are much more active than bulk V₂O₅. For WO₃, a series of added row reconstructions were observed as the epitaxial films were reduced. The effect of these structures on surface chemistry was characterized by studying 1-propanol adsorption. The results indicated that the structure of the WO₃ surface did not alter its catalytic function but had a strong effect on reaction kinetics. As an example of a system where catalysts prevent the formation of toxic species, the reactivity of oxidized Pd surfaces used in CH₄ catalytic combustion were studied. An ordered PdO-like monolayer was found to be less reactive towards CO than adsorbed O on Pd. On the other hand, the PdO layer favored a lower activation energy C₃H₆ oxidation pathway. The results indicated that Pd oxidation reduces the sticking coefficient of reactive species but once molecules adsorb, the oxide surface can reduce the activation energy for subsequent reaction.     

Singlet versus triplet dynamics of β-carotene studied by quantum control spectroscopy

Biomolecules very often present complex energy deactivation networks with overlapping electronic absorption bands, making their study a difficult task. This can be especially true in transient absorption spectroscopy when signals from bleach, excited state absorption and stimulated emission contribute to the signal. However, quantum control spectroscopy can be used to discriminate specific electronic states of interest by applying specifically designed laser pulses. Recently, we have shown the control of energy flow in bacterial light-harvesting using shaped pump pulses in the visible and the selective population of pathways in carotenoids using an additional depletion pulse in the transient absorption technique. Here, we apply a closed-loop optimization approach to β-carotene using a spatial light modulator to decipher the energy flow network after a multiphoton excitation with a shaped ultrashort pulse in the near-IR. After excitation, two overlapping bands were detected and identified as the S₁ state and the first triplet state T₁. Using the transient absorption signal at a specific probe delay as feedback, the triplet signal could be optimized over the singlet contribution.     

Effects of trapped electrons on the line shape in emission Mössbauer spectra

To explain line broadening in emission Mössbauer spectra as compared to the corresponding absorber measurements, the model of trapped electrons has been proposed. Auger electrons (emitted, e.g. after electron capture by ⁵⁷Co or after the converted isomeric transition of ^119mSn), as well as secondary electrons, may be trapped in the proximity to the nucleogenic ion. Electrons captured by lattice traps at different distances from the daughter ion induce an asymmetric distribution of quadrupole splitting in the resulting emission spectra, as shown in a few examples. This model is supported by estimates of quadrupole splitting values which may be caused by such trapped electrons located at specified distances from the nucleogenic atom.     

Spectroscopic and X-ray diffraction study of high Tc epitaxial YBCO thin films obtained by pulsed laser deposition

We report spectroscopic characterization of epitaxial YBCO thin films grown on LaAlO₃ by pulsed laser deposition. Raman spectroscopy and spectroscopic ellipsometry were used for film characterization and the results were correlated with X-ray diffraction measurements. The mentioned techniques allowed us to analyze crystallographic, micro-structural, and morphological properties of YBCO thin films. We also demonstrated that relatively low resolution Raman spectroscopy and spectroscopic ellipsometry are reliable techniques for a rapid and non-destructive characterization of epitaxial YBCO thin films.     

Analysis of reflectance and modulation spectroscopic lineshapes in optoelectronic device structures

We discuss the spectral lineshapes of reflectance and modulated reflectance (MR) measurements on optoelectronic device structures such as epi-layers, quantum wells (QWs), vertical-cavity surface emitting-lasers (VCSELs) and resonant-cavity light-emitting diodes (RCLEDs). We consider the various methods for the extraction of built-in electric fields and band-gap energies from Franz-Keldysh oscillations (FKO), using the example of a tensilely strained InGaAs QW system, whose InGaAsP barriers yield strong FKO. We describe how critical point transition energies can be easily obtained by eye from Kramers-Kronig (KK) transforms of low field or QW modulation spectra, using the example of the modulated transmittance spectra of dilute-nitrogen InGaAsN p-i-n structures. We also discuss how the ordinary reflectivity spectrum, usually acquired at the same time as the MR signal, may also be exploited to extract layer thicknesses and compositions, and information about the active QW absorption spectrum in VCSEL and RCLED structures.