Extended Born-Oppenheimer equation for a three-state system

We present explicit forms of nonadiabatic coupling (NAC) elements of nuclear Schrodinger equation (SE) for a coupled three-state electronic manifold in terms of mixing angles of real electronic basis functions. If the adiabatic-diabatic transformation (ADT) angles are the mixing angles of electronic bases, ADT matrix transforms away the NAC terms and brings diabatic form of SE. ADT and NAC matrices are shown to satisfy a curl condition with nonzero divergence. We have demonstrated that the formulation of extended Born-Oppenheimer (EBO) equation from any three-state BO system is possible only when there exists a coordinate-independent ratio of the gradients for each pair of mixing angles. On the contrary, since such relations among the mixing angles lead to zero curl, we explore its validity analytically around conical intersection(s) and support numerically considering two nuclear-coordinate-dependent three surface BO models. Numerical calculations are performed by using newly derived diabatic and EBO equations and expected transition probabilities are obtained.     

Microindentation Hardness of Nanostructured Thermoplastic Materials

Summary: The micromechanical behaviour of various thermoplastics based nanocomposites was investigated with the aid of the microindentation technique. The materials studied were microphase separated styrene-butadiene block copolymer systems and several thermoplastics reinforced with nano-sized fillers having variable dimensionality. It was found that the microhardness behaviour of the nanocomposites studied was strongly influenced by the dimensionalities of the filler. Due to large surface to volume-ratio one- and two-dimensional fillers exhibit a far better reinforcing behaviour than the three dimensional ones. In case of nanostructured block copolymers, the microhardness is not determined by the total polystyrene (PS)/polybutadiene (PB) composition alone but diminishes gradually in presence of freely standing dangling polybutadiene chains even if the morphology of the systems remains unaltered.     

High dimensional model representation for stochastic finite element analysis

This paper presents a generic high dimensional model representation (HDMR) method for approximating the system response in terms of functions of lower dimensions. The proposed approach, which has been previously applied for problems dealing only with random variables, is extended in this paper for problems in which physical properties exhibit spatial random variation and may be modelled as random fields. The formulation of the extended HDMR is similar to the spectral stochastic finite element method in the sense that both of them utilize Karhunen–Loève expansion to represent the input, and lower-order expansion to represent the output. The method involves lower dimensional HDMR approximation of the system response, response surface generation of HDMR component functions, and Monte Carlo simulation. Each of the low order terms in HDMR is sub-dimensional, but they are not necessarily translating to low degree polynomials. It is an efficient formulation of the system response, if higher-order variable correlations are weak, allowing the physical model to be captured by the first few lower-order terms. Once the approximate form of the system response is defined, the failure probability can be obtained by statistical simulation. The proposed approach decouples the finite element computations and stochastic computations, and consecutively the finite element code can be treated as a black box, as in the case of a commercial software. Numerical examples are used to illustrate the features of the extended HDMR and to compare its performance with full scale simulation.     

An efficient multi-use multi-secret sharing scheme based on hash function

In this work, a renewable, multi-use, multi-secret sharing scheme for general access structure based on the one-way collision resistant hash function is presented in which each participant has to carry only one share. As it applies the collision resistant one-way hash function, the proposed scheme is secure against conspiracy attacks even if the pseudo-secret shares are compromised. Moreover, high complexity operations like modular multiplication, exponentiation and inversion are avoided to increase its efficiency. Finally, in the proposed scheme, both the combiner and the participants can verify the correctness of the information exchanged among themselves.     

Micellar catalyzed redox reactions of bilirubin in CTAB medium. A pulse radiolysis study

The reaction of CO with bilirubin which is not detectable in homogeneous aqueous medium proceeds almost with diffusion controlled rate in CTAB micellar system. This could be explained on the basis of catalysis caused by the possible electrostatic surface potential of cationic CTAB Micelles. The rate constant for the oxidation of bilirubin by haloperoxyl radicals have been shown to increase with increasing solvent polarity. Although the polarity effect was small, it followed a trend in the expected direction. Micellar effect was not observed in the oxidation reactions when alcohol was present in high concentration. But a small increase in the rate constant was observed when alcohol concentration was lower. © 1994 John Wiley & Sons, Inc.     

Pervaporation separation of aqueous chlorophenols by a novel polyurethane urea–poly (methyl methacrylate) interpenetrating network membrane

A novel polymer membrane system consisting of interpenetrating network (IPN) of hydroxy terminated polybutadiene (HTPB) based polyurethane urea (PUU)–poly (methyl methacrylate) (PMMA) has been designed and developed as highly permselective membrane for pervaporation separation of toxic p-chlorophenol and 2,4-dichlorophenol from their dilute aqueous solutions. It was observed that 3 ppm 2,4-dichlorophenol in water could be reduced to 0.3 ppm 2,4-dichlorophenol using a PUU–PMMA IPN membrane of 28 cm² area and 150 μm thickness. This membrane has shown high selectivity towards p-chlorophenol and 2,4-dichlorophenol at very low concentration in feed. Feed concentration of p-chlorophenol was varied from 1000 to 7000 ppm and that of 2,4-dichlorophenol was varied from 3 to 4000 ppm. Fifty seven percent 2,4-dichlorophenol in permeate was obtained from 3 ppm concentration in feed compared to 87% 2,4-dichlorophenol in permeate from 1000 ppm in feed. Pervaporation studies were carried out by varying the temperature of feed, membrane thickness and PMMA content in the membrane. The results of this investigation have revealed that these membranes would be suitable for separation of chlorophenols from industrial effluents.     

Redox reactions of 3'-azido-3'-deoxythymidine (AZT) and interaction of its OH-derived radical with bilirubin and riboflavin: A pulse radiolysis study

Using the technique of pulse radiolysis, redox studies of 3-azido-3-deoxythymidine (azidothymidine or AZT) with hydrated electron and hydroxyl radicals, generated in phosphate-buffered aqueous medium, are reported. The hydrated electron reacts with AZT (k = 1.9 × 10¹⁰ dm³ mol^-1 s^-1) to generate transients with absorption maxima at 300 and 340 nm. The hydroxyl radical adds to AZT to generate transients with absorption maxima at 310 and 365 nm, with formation rate constant of 9.0 × 10⁹ dm³ mol^-1 s^-1 as observed at 310 and 365 nm. The secondary radical 6-hydroxy-5-yl-azidothymidine, formed in the reaction of AZT with hydroxyl radical, reacts with bilirubin to give a transient of bilirubin with bimolecular rate constant of 1.8 × 10⁸ dm³ mol^-1 s^-1. In the reaction of hydroxyl radical with AZT/riboflavin pair, an ^. H atom transfer from riboflavin to the 6-hydroxy-5-yl-azidothymidine is observed. Reactions of OH-derived radicals of thymine with bilirubin and riboflavin are similar to that of AZT. Possible mechanisms are proposed for the observed reactions.     

Formation of linkage isomers via the substitution of halides by selenocyanate in ruthenium(III) complexes

Summary Substitution of the halide ion of [Ru(NH₃)₅X]²⁺ (X=Cl^– or Br^–) by SeCN^– was monitored spectrophotometrically between 45 and 60° C in aqueous medium. The pseudo-first order rate constants were evaluated by Guggenheim's procedure, which shows linearity for 2–3 half-lives. The rate increases linearly with [SeCN^–] and all the plots have a positive intercept on the rate axis. The SeCN^–-independent path represents aquation and the SeCN^–-dependent path represents anation of the aqua complex with simultaneous formation of two isomeric (the N bonded and the Se bonded) products. The formation of the isomeric products is entropy controlled.     

Reaction between [Ru3(CO)10(μ-dppm)] (dppm = Ph2PCH2PPh2) and Te2(C6H4OEt-4)2: X-ray crystal structure of [Ru2(CO)6{μ-C6H4PPh(CH2)PPh}]

Treatment of [Ru₃(CO)₁₀(-dppm)] (1) with the ditelluride Te₂(C₆H₄OEt-4)₂ in refluxing toluene afforded the new aryltellurol bridged complex [Ru₂(CO)₄(-TeC₆H₄OEt-4)₂ (-dppm)] (2) together with three known complexes [Ru₄(CO)₈(-CO)(₄-Te)₂(-dppm)] (3), [Ru₂(CO)₆{-CH₂PPh(C₆H₄)PPh}] (4), and [Ru₂(CO)₆{-C₆H₄PPh(CH₂)PPh}] (5). All the four complexes were characterized by spectroscopic methods, including an X-ray structure determination for 5. Complex 5 crystallizes in the monoclinic space group P2₁/c with a = 13.650(2), b = 9.995(2), c = 18.929(3) Å, = 97.49(2)°, V = 2560.4(8) ų, and Z = 4. In this complex the two ruthenium atoms are bridged by the phosphino-phosphide ligand C₆H₄PPh(CH₂)PPh which is attached to one Ru by the C₆H₄ group and a P atom while to the other Ru by both the two P atoms. Both the ruthenium atoms show distorted octahedral geometry. The Ru—Ru bond length is 2.8719(7) Å.