The structures and electronic absorption spectra of substituted phenyldiacetylenes: experimental and theoretical studies

The results of experimental and theoretical investigation of the electronic absorption spectra of substituted phenyldiacethylenes are presented. The bands in the experimental spectra were assigned in detail using quantum chemical calculations of the electronic structures and spectra of the molecules. The influence of the interaction of the substituents on the spectral parameters of the systems under study was analyzed. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1947–1953, October, 2007.     

A spectro-microscopic study of the reactive phase separation of Au + Pd and O on Rh(1 1 0)

Reorganization of Au + Pd submonolayers on a Rh(1 1 0) surface occurring during the water formation reaction has been observed and characterized by low energy electron microscopy (LEEM) and X-ray photoemission electron microscopy (XPEEM). The results demonstrate segregation of Au + Pd and oxygen into separate surface phases, the morphology and size of the O and Au + Pd patterns being governed by the reaction parameters and adsorbate coverage. At moderate Au + Pd coverages and temperatures in the range 760-860 K, lamellar periodic Au + Pd/O micro-structures are generated. The results are interpreted in terms of kinetic and thermodynamic considerations.     

Monte Carlo simulations of oscillations, chaos and pattern formation in heterogeneous catalytic reactions

Experimental studies employing surface science methods indicate that kinetic oscillations, chaos, and pattern formation in heterogeneous catalytic reactions often result from the interplay of rapid chemical reaction steps and relatively slow complementary processes such as oxide formation or adsorbate-induced surface restructuring. In general, the latter processes should be analysed in terms of theory of phase transitions. Therefore, the conventional mean-field reaction–diffusion equations widely used to describe oscillations in homogeneous reactions are strictly speaking not applicable. Under such circumstances, application of the Monte Carlo method becomes almost inevitable. In this review, we discuss the advantages and limitations of employing this technique and show what can be achieved in this way. Attention is focused on Monte Carlo simulations of CO oxidation on (1 0 0) and (1 1 0) single-crystal Pt and polycrystal Pt, Pd and Ir surfaces and of NO reduction by CO and H₂ on Pt(1 0 0). CO oxidation on supported nanometre-sized catalyst particles and NO reduction on composite catalysts are also discussed. The results show that with current computer facilities the MC technique has become an effective tool for analysing temporal oscillations and pattern formation on the nanometre scale in catalytic reactions occurring on both single crystals and supported particles.     

On the effect of cure cycle parameters and dopants on pre and post irradiation annealing response of CR-39 track detectors

The effect of additives and cure cyle parameters on pre and post irradiation annealing characteristics of CR-39 detectors has been investigated. Effect of pre and post irradiation annealing on bulk etch rate, sensitivity, track diameter and etching behaviour of various CR-39 detectors has been investigated.     

Surface chemistry of alkyl and perfluoro ethers: a FTIR and ab initio study of adsorption and decomposition of CF3OCF3 on an Al2O3 surface

The adsorption and thermal decomposition of perfluorodimethyl ether, (CF₃)₂O, on a high-surface-area Al₂O₃ surface was investigated by FTIR under both vacuum and pressure conditions. IR spectra in the 4000-1050 cm⁻¹ range were collected and the spectral assignments were assisted by quantum chemical ab initio calculations. The spectral evidence indicated that (CF₃)₂O decomposed to form adsorbed fluoroformate, FCOO (ads). Increases of temperature (up to 525 K) caused the FCOO (ads) to convert to hydrogen formate, HCOO (ads). Surface hydroxyl groups participated in the decomposition of (CF₃)₂O and the conversion of FCOO (ads) to HCOO (ads). A decomposition mechanism is proposed.     

Monte Carlo simulations of catalytic CO oxidation on fractal surfaces of dimension between two and three

We present a method for generating fractal surfaces of dimension between two and three. By using the method, five fractal surfaces with dimension 2.262, 2.402, 2.524, 2.631, and 2.771 are created. For each of these surfaces, the reaction of carbon monoxide and oxygen is simulated by using a Monte Carlo method based on the ZGB model [Phys. Rev. Lett. 24 (1986) 2553]. The results show that the catalytic CO oxidation proceeds more efficiently on a surface with higher fractal dimension. It is also found that as the fractal dimension of the surface becomes higher, the first-order kinetic phase transition point (y₂) is shifted to a higher partial pressure of CO. This implies that poisoning of the catalyst surface due to CO segregation sets in at a higher CO partial pressure for surfaces with more complexity.     

中能重离子碰撞中的同位旋分馏过程

利用同位旋相关的量子分子动力学模型研究了中能重离子碰撞中同位旋分馏过程.研究结果表明自由粒子中质比与碎片中质比的比值即同位旋分馏强度灵敏地依赖于对称势,而对同位旋相关核子–核子碰撞截面的依赖很弱.同位旋分馏对对称势的灵敏主要来自于气相部分,而液相部分对对称势不够灵敏.气相部分灵敏地依赖于对称势是直接造成同位旋分馏强度对对称势灵敏的主要原因.同时还讨论了各种液相部分的取法,其结果表明不同取法对以上结论的影响不大.因此理论结果与实验数据可以直接比较从而提取对称势的知识.并对引发同位旋分馏的动力学的起因进行了分析和讨论.     

塔里木河干流区地方性氟病区水化学成分的多元分析

本文运用相关分析、回归分析及Ｒ－型系统聚类分析等方法，研究了里木河干流地区的地方性氟中毒病区内，氟斑牙患病率与饮用水中氟元素及其它化学成分的定量关系，并建立了生活饮用水中氟元素与其它化学成分的回归计算模型，提示了区域内氟斑牙治病的主导因素以及水体中各化学成分和化学性质指标间的相互关系，为探求饮用水型地方性氟中毒的病因提供了科学依据。     

Chemical effect on the K shell fluorescence yield of Fe, Mn, Co, Cr and Cu compounds

Chemical effects on the K shell fluorescence yields of Fe, Mn, Co, Cr and Cu compounds were investigated. Samples were excited using 59.5 keV energy photons from a²⁴¹ Am radioisotope source. K X-rays emitted by samples were counted by a Si(Li) detector with a resolution 160 eV at 5.9 keV. Chemical effects on the K shell fluorescence yields (ωk) for Fe, Mn, Co, Cr and Cu compounds were observed. The values are compared with theoretical, semiempirical fit and experimental ones for the pure elements.