Sharif Digital Repository

A combined experimental and computational study was carried out on the gas phase pyrolysis reaction of diallylsulfoxide. Allylalcohol and Thioacrolein were detected as the major products during a unimolecular reaction. Experimental kinetic studies were carried out via a static system over the pressure of 21-55 torr and temperature of 435.2-475.1 K. Based on the experiments, the reaction is homogeneous and proceeds through a zwitterionic intermediate. Computational studies at the DFT (B3LYP) and QCISD(T) levels with 6-311++G(d,p) basis set indicated a two-step concerted pathway as the possible route. Comparison between the experimental and theoretical activation parameters for the most... 

The potential energy surface of the reaction C3H 5SCH2X→C3H6+XCH=S was studied for the various X substitutions (X=CH3, H, Cl, F) at the high level of the theory (G3MP2 method) using the 6-31G(d) basis set. It was demonstrated that CH3, H, Cl and F substitution, respectively, accelerates the reaction (This order for the substitutions will be called X=CH3-to-F throughout this paper). Barrier height changes from ΔE≠=167. 76 to 148.63 kJ mol-1, because of the electronic effects introduced upon the substitution. It was shown that the X=CH3-to-F substitution in the C6-position posses two types of contribution to the calculated energy barriers and bond lengths at the transition state (TS). First,... 

The mechanism and kinetic aspects of the retro-ene reaction of the Allyl n-propyl sulfide and its deuterated derivative were studied using four different types of density functional theory methods with eight different levels of the basis sets. The activation energies were determined at 550.65 K. As a consequence of our calculations, a transition state is concluded that consists of a polar six-center cyclic structure. We found that the combination B3PW91/6-311++G** produces activation energy values closer to the experimental ones, but the simpler combination B3LYP/6-31G* produces excellent values too in less time. Our calculations show that the activation parameters obtained from the B3... 

A combination of the experimental and theoretical study was carried out on the reaction mechanism associated with the pyrolysis of 2-pyridylacetic acid in the gas phase. Methylpyridine and carbon dioxide were analyzed as the products, using a static system over the pressure range of 18-55 torr and the temperature of 541.2-583.4 K. The experimental kinetic data show that the pyrolysis process is homogeneous, unimolecular and proceeds through a concerted mechanism. Theoretical studies at the B3LYP level using the 6-31G* basis set confirmed an asynchronous concerted mechanism for the reaction. Computed kinetic and activation parameters are in good agreement with the experimental one. © 2006... 

The mechanism and kinetic aspects of the retro-ene reaction of allyl n-butyl sulfide and its deuterated derivative were studied using four different types of density functional theory (DFT) methods with eight different levels of the basis sets. Vibrational frequency analysis confirmed that the stationary points include the transition state (TS) structure with only one imaginary frequency. Mechanistic studies on the retro-ene process rejected the step-wise mechanism and confirmed that the reaction proceeds through a six-centered cyclic transition state. Theoretical calculations show that propene elimination from the reactant can occur through an asynchronous concerted mechanism. A primary... 

AISI 4340 steel bars were heated at 900 °C for one hour, annealed at 738 °C for different durations and oil-quenched in order to obtain dual phase steels with different ferrite volume fractions. A 3% prestrain at the temperature range of 150-450 °C was then imposed to the samples, and room temperature tensile tests were carried out, afterwards. Results indicate that the maximum values for both yield and ultimate tensile strength would exist for the samples pre-strained at the temperature range of 250-300 °C. Also, a sudden drop of the ductility was observed at the mentioned temperature range. The observed behavior might be attributed to the occurrence of dynamic strain aging taken place at... 

A joint theoretical and experimental study of the kinetic and mechanism of the rearrangement of allyl p-tolyl ether was performed in order to study the kinetic and mechanism of the reaction. Experimental studies were performed in gas phase over a temperature range of 493.15–533.15 K. The experimental Arrhenius parameters of this reaction were measured to be Ea = 36.08 kcal mol−1, ΔS# = −7.88 cal mol−1 K−1, and Log A = 11.74, experimentally. Using GC for the mixture of the reaction with and without cyclohexene demonstrated that the reaction is clean without any radical intermediates. The experimental results show that the studied reaction is unimolecular and proceeds through a concerted... 

Various ionic liquids (ILs) and their mixtures were coated on the Pt/Al2O3 catalyst and the resulting IL-coated catalysts were used in the synchronous hydrogenation of cyclohexene and acetone. The rate constant (k) and selectivity (S) toward CO hydrogenation were determined for several catalysts in various solvents. The solvatochromic parameters (ETN, normalized polarity parameter; π*, dipolarity-polarizability; β, hydrogen-bond acceptor basicity; α, hydrogen-bond donor acidity) were determined for the used ILs and solvents and the obtained selectivities were modeled based on the solvatochromic parameters of the IL layer and bulk solvent while using the Multiparameter Linear Regression (MLR)... 

In this paper we study slotted ALOHA random access optical code division multiple access packet-switching networks with a chip-level receiver structure. We use generalized optical orthogonal codes (GOOCs) and the overlapping pulse position modulation (OPPM) signaling technique to improve system performance. The impact of physical layer parameters such as the GOOC cross-correlation value and the OPPM overlapping index on key performance benchmarks such as network throughput and delay are analyzed. We also study the stability of the network based on the number of backlogged users, using the expected state drift. It has been shown that using GOOC instead of strict optical orthogonal codes... 

In this paper, we study the effect of non-Poisson traffic patterns on energy consumption for IEEE 802.16e nodes while operating in the sleep mode. In the sleep mode, a Mobile Subscribe Station (MSS) sleeps for a sleep interval and wakes up at the end of this interval in order to check buffered packet(s) at Base Station (BS) destined to it. If there is no packet, the MSS increases the sleep window up to the maximum value and sleeps again. For a more general traffic pattern (rather than Poisson), we evaluate the average power consumption. Based on our analysis, we conclude that traffic pattern plays an important role in power consumption. ©2007 IEEE  

Electrochemical oxidation of acetaminophen (N–acetyl–p–aminophenol) (1) has been studied in the presence of dimethylamine (2) as a nucleophile in aqueous solution, by means of cyclic voltammetry and controlled-potential coulometry. The results indicate the participation of electrochemically generated N-acetyl-p-quinoneimine (1a) in Michael reaction with dimethylamine (2). Based on ECE mechanism, the observed homogeneous rate constant (kobs) of the above mentioned reaction is estimated by comparing the experimental cyclic voltammograms with the digital simulated results. Further more; kinetics and mechanism of the reaction were studied with ab initio calculation, Monte Carlo and QM/MM... 

Selective oxidations of alkenes were investigated using molecular oxygen in aqueous solution under mild conditions. Colloidal gold nanoparticles are particularly versatile catalysts for oxidation reaction with exceptionally high efficiency and significant selectivity. Gold nanorods (Au NRs) exhibited a slightly enhanced activity compare to gold nanospheres  

Aluminum 6xxx and 7xxx series are among the most commonly used alloys in industrial applications whereas their joining and welding using conventional fusion-based weld processes are very difficult. In this paper, friction stir welding process of dissimilar AA6061-T6 and AA-7277-T6 aluminum plates was investigated. The effects of tool travers and rotational speeds and the type of material located in the advanced side (AS) or retreating side (RS) of weldment were studied experimentally on the mechanical and metallurgical characteristics of the joint. Macro- and microstructure pictures of weld region were used to evaluate the quality of the weld and defect detections. Tensile strength tests and... 

As massively multiuser virtual environments (MMVEs) expand in terms of size and user population, they tend toward using P2P architectures as a way to provide scalability without the need for large centralized resources. Distributed hash table (DHT)-based networks have been introduced as a promising option for overlay-based distributed massively multiuser virtual environment applications. However, overlay latency stretch seriously affects MMVE performance where QoS is crucial for real-time user collaboration. This work includes a series of efforts in the alleviation of such undesired latency. Our approach to latency mitigation consists of two phases. First, we propose a position-based ID... 

This article has been retracted at the request of the Editorial Board of Current Applied Physics. Please see Elsevier Policy on Article Withdrawal (http://www.elsevier.com/locate/withdrawalpolicy). Reason: The authors have plagiarized part of a paper that had already appeared in J. Phys. Chem. B, 109 (2005) 3334–3339: “Changes of Coupling between the Electrodes and the Molecule under External Bias Bring Negative Differential Resistance, by Xingqiang Shi, Xiaohong Zheng, Zhenxiang Dai, Yang Wang, and Zhi Zeng”. One of the conditions of submission of a paper for publication is that authors declare explicitly that their work is original and has not appeared in a publication elsewhere. Re-use...