Formation of Superheavy Elements: Study Based on Dynamical Approach

Using multi-dimensional Langevin equations for the probability distribution of the distance between the surfaces of two approaching nuclei, we have studied the formation of superheavy elements via calculation of evaporation and fission cross sections of these elements. Evaporation residue cross sections have been calculated for the 1n, 2n, 3n, 4n, and 5n evaporation channels using one and four dimensional Langevin equations for the ⁴⁸Ca+²²⁶Ra, ²³²Th, ²³⁸U, ²³⁷Np, ^{239,240,242,244}Pu, ²⁴³Am, ^245,248Cm, ²⁴⁹Bk, and ²⁴⁹Cf reactions. Our results show that with increasing dimension of Langevin equations the evaporation residue cross section is increased. Also, obtained results based on fourdimensional Langevin are in better agreement with experimental data in comparison with one-dimensional model.     

Using nucleators to control freckles in unidirectional solidification

Buoyancy-induced fluid flow, which is responsible for most forms of macro-segregation and channel-type segregates in castings, is not directly controllable. If left uncontrolled, natural convection will contribute to non-uniform distribution of alloy constituents and grain structure during solidification of a casting. Non-uniform distribution of chemical composition and physical structure in an alloy casting can significantly affect the reliability of mechanical components. Therefore, materials with acceptable defects can be produced only by trial-and-error and their acceptability is determined by costly inspections. We present a novel technique to control the formation of chimneys and resulting freckles in the mushy zone during the solidification of ammonium chloride that is cooled from below. This is done by placing metallic nucleators in particular arrangements on the bottom cooling plate. With this technique, freckles in a casting might be avoided and/or be forced to form where stresses are expected to be lower during use of the part.The objective of this study is to investigate the effects of the arrangement, spacing, and size of the nucleators on finger formation, plume structure, and the solidification process. Results showed that it is possible to obtain a relatively large area free of channel-segregates in a metal analog directionally solidified upward by placing nucleators in certain arrangements at the bottom of the casting. The outcomes of this study will serve as a baseline for subsequent investigations that will examine the solidification of binary alloys, and could be used to test and develop mathematical and numerical models.     

Survey of Double Vertex Graphs

 Let G be a (V,E) graph of order p≥2. The double vertex graph U ₂ (G) is the graph whose vertex set consists of all 2-subsets of V such that two distinct vertices {x,y} and {u,v} are adjacent if and only if |{x,y}∩{u,v}|=1 and if x=u, then y and v are adjacent in G. For this class of graphs we discuss the regularity, eulerian, hamiltonian, and bipartite properties of these graphs. A generalization of this concept is n-tuple vertex graphs, defined in a manner similar to double vertex graphs. We also review several recent results for n-tuple vertex graphs. Received: October, 2001 Final version received: September 20, 2002 Dedicated to Frank Harary on the occasion of his Eightieth Birthday and the Manila International Conference held in his honor     

Catalytic role of gold in gold-based catalysts: a density functional theory study on the CO oxidation on gold

Gold-based catalysts have been of intense interests in recent years, being regarded as a new generation of catalysts due to their unusually high catalytic performance. For example, CO oxidation on Au/TiO(2) has been found to occur at a temperature as low as 200 K. Despite extensive studies in the field, the microscopic mechanism of CO oxidation on Au-based catalysts remains controversial. Aiming to provide insight into the catalytic roles of Au, we have performed extensive density functional theory calculations for the elementary steps in CO oxidation on Au surfaces. O atom adsorption, CO adsorption, O(2) dissociation, and CO oxidation on a series of Au surfaces, including flat surfaces, defects and small clusters, have been investigated in detail. Many transition states involved are located, and the lowest energy pathways are determined. We find the following: (i) the most stable site for O atom on Au is the bridge site of step edge, not a kink site; (ii) O(2) dissociation on Au (O(2)-->2O(ad)) is hindered by high barriers with the lowest barrier being 0.93 eV on a step edge; (iii) CO can react with atomic O with a substantially lower barrier, 0.25 eV, on Au steps where CO can adsorb; (iv) CO can react with molecular O(2) on Au steps with a low barrier of 0.46 eV, which features an unsymmetrical four-center intermediate state (O-O-CO); and (v) O(2) can adsorb on the interface of Au/TiO(2) with a reasonable chemisorption energy. On the basis of our calculations, we suggest that (i) O(2) dissociation on Au surfaces including particles cannot occur at low temperatures; (ii) CO oxidation on Au/inactive-materials occurs on Au steps via a two-step mechanism: CO+O(2)-->CO(2)+O, and CO+O-->CO(2); and (iii) CO oxidation on Au/active-materials also follows the two-step mechanism with reactions occurring at the interface.     

Quantum delocalization of hydrogen in the Li2NH crystal

By mapping out potential energy surfaces from density-functional theory (DFT) and solving a protonic Schr?dinger equation, we find that the H atom in a unit cell of the Li2NH crystal shows remarkably strong quantum behavior, leading to the delocalization of H over six octahedral sites around each N. This can be rationalized in terms of rapid coherent tunneling among these equivalent octahedral sites. Structural and dynamical consequences of our finding are discussed. Since the Li-N-H compounds are considered promising candidates for H-storage, understanding of these fundamental properties will be useful toward improving the performance of the material.     

A distinct intermediate of RNase A is induced by sodium dodecyl sulfate at its pK(a)

The chemical denaturation of RNase A was found to be mediated by sodium dodecyl sulfate (SDS) at various pH. The characterization of the unfolding pathway was investigated by spectrophotometry and differential scanning calorimetry (DSC), and was analyzed by multivariate curve resolution (MCR) as a chemometric method. The spectrophotometric titration curve of RNase A upon interaction with SDS indicated a distinct complex intermediate in glycine buffer at pH 3.3. This was accompanied with the catalytic activation of the enzyme and was concurrent with maximum population of the intermediate, determined by MCR. This was confirmed by the DSC profile of RNase A in the presence of SDS, indicated by two transitions in thermal unfolding. The kinetic data on the unfolding process of RNase A upon addition of SDS showed a two-phase pathway under the same conditions. The intermediate appeared at low pH especially at the pK_a of SDS (pH 3.3). These results provide strong evidence of the influence of low pH (around the pK_a of SDS) on the existence of an intermediate upon interaction of RNase A with SDS.     

Phase Transition of a Structure II Cubic Clathrate Hydrate to a Tetragonal Form

The crystal structure and phase transition of cubic structure II (sII) binary clathrate hydrates of methane (CH₄) and propanol are reported from powder X‐ray diffraction measurements. The deformation of host water cages at the cubic–tetragonal phase transition of 2‐propanol+CH₄ hydrate, but not 1‐propanol+CH₄ hydrate, was observed below about 110 K. It is shown that the deformation of the host water cages of 2‐propanol+CH₄ hydrate can be explained by the restriction of the motion of 2‐propanol within the 5¹²6⁴ host water cages. This result provides a low‐temperature structure due to a temperature‐induced symmetry‐lowering transition of clathrate hydrate. This is the first example of a cubic structure of the common clathrate hydrate families at a fixed composition.     

Effects of CO2 content on the activity and stability of nickel catalyst supported on mesoporous nanocrystalline zirconia

The effects of carbon dioxide content on the catalytic performance and coke formation of nickel catalyst supported on mesoporous nanocrystalline zirconia with high surface area and pure tetragonal crystalline phase were investigated in methane reforming with carbon dioxide. The samples were characterized by XRD, BET, TPR, TPO, TPH, TEM, and SEM techniques. The catalyst prepared showed high surface area and a mesoporous structure with a narrow pore size distribution. The obtained results revealed that the increase in CO2 content increased the methane conversion and stability of the catalyst and significantly reduced the coke deposition. The TPH analysis showed that several species of carbon with different reactivities toward hydrogenation were deposited on the spent catalysts employed under different CO2 contents.