Sharif Digital Repository

Density functional theory is used in a spin-polarized plane wave pseudopotential implementation to investigate molecular oxygen adsorption and dissociation on graphite and nickel-doped graphite surfaces. Molecular oxygen physisorbs on graphite surface retaining its magnetic property. The calculated adsorption energy is consistent with the experimental value of 0.1eV. It is found that substituting a carbon atom of the graphite surface by a single doping nickel atom (2.8% content) makes the surface active for oxygen chemisorption. It is found that the molecular oxygen never adsorbs on doping nickel atom while it adsorbs and dissociates spontaneously into atomic oxygens on the carbon atoms... 

The adsorption and dissociation of H2O2 on small PdxM3-x (M=Pt, Cu; x = 1-3) clusters is investigated using the B3PW91 hybrid density functional method. Natural bond orbitals are analysed to obtain partial charges on atoms, dipole moments, bond orders, and hybrid orbitals of the PdxM3-x-H2O2 systems. The calculated adsorption energies are in the range of -0.32 to -2.12 eV. Generally, H2O2 adsorbs on top positions through one of its oxygen atoms and only in a few cases reacts with the cluster through both oxygen and hydrogen sides. In the latter case the cluster sites which are negatively charged interact with the hydrogen atoms. Interestingly, on the triplet Pd2Pt cluster, H2O2 dissociates... 

Theoretical study of carbon monoxide adsorption on SixGe4 - x(x = 0-4) nano-clusters has been carried out using advanced hybrid meta density functional method of Truhlar (MPW1B95). MG3 semi-diffuse (MG3S) and correlation consistent valence basis sets with relativistic core potential were employed to improve the results. The agreement of the calculated ionization and dissociation energies with experimental values validates the reported structures of nano-clusters and justifies the use of hybrid meta density functional method. The geometry, adsorption energy, charge distribution, and vibrational frequency of CO adsorption on all possible structures were investigated. The maximum vibrational... 

Polyols were used as model ligands for Mg2+, Ca2+, and Zn2+ complexes to study the role of the hydrogen bond network on the metal binding affinity and modulation of successive pKa values using density functional theory. The results confirm that the acidity of polyols dramatically increases upon metal complexation in the order Zn2+ > Mg2+ > Ca2+. For example, the three H-site positions in the hydroxyl groups of the heptaol, bound to Zn2+, are 11.2, 29.9, and 30.9 pKa units (in methanol) more acidic than those of pure heptaol. This acidity enhancement leads to making polyols as good ligands toward complexation. For instance, the formation constants of the heptaol in the presence of Zn2+, Mg2+,... 

Because of the possibility of various types of vacancies in cementite due to its crystalline structure, the focus of this paper was only on vacancies. In this regard, the formation energies of single, two, three and four vacancies of over than 120 different cases were calculated using first-principles method. For the case of single vacancy, the results were in three values of ~1.63, 1.39 and 0.78 eV according to iron vacancies at general positions, iron vacancies located on mirror planes and carbon vacancies in the interstitial positions, respectively. The results for the case of two, three and four vacancies were between from 2.10 to 3.34 eV, from 3.92 to 5.10 eV and from 4.77 to 6.33 eV,... 

Using cluster-based density functional theory we investigate adsorption configurations of an acetophenone molecule on a Si(001) surface and their follow-up proton transfer processes. We examine two possible types of dative-adsorption configurations, up-right standing and flat, as well as compute their follow-up kinetically preferable on-dimer, interdimer, and inter-row proton transfers. Energetics of possible conversions between the achieved adsorption configurations are computed as well. Using all the data obtained, we theoretically illustrate reaction pathways leading to detached hydrogen positions captured in STM imaging of a Si(001) surface exposed to acetophenone vapor at room... 

CdS nanocrystals were thermochemically (thermally activated) synthesized thorough the reaction between CdSO4 and Na2S 2O3 in an aqueous solution. Thioglycolic Acid (TGA) was used as the capping agent and catalyst of the reaction. The method was based on heat activated dissociation of Na2S2O3 and controllable release of S and free electrons in the solution. CdS NCs were formed by heating the sample solution at 96 C for 1 h. The results of optical spectroscopy and transmission electron microscopy demonstrated round shape NCs with sizes about 3.0 nm. The nanocrystals were also luminescent and represented a broad emission with a peak located at 515 nm and FWHM of 160 nm. Several samples were... 

Mononuclear nonheme iron containing systems are versatile and vital oxidants of substrate hydroxylation reactions in many biosystems, whereby the rate constant of hydroxylation correlates with the strength of the C-H bond that is broken in the process. The thermodynamic reason behind these correlations, however, has never been established. In this work results of a series of density functional theory calculations of substrate hydroxylation by a mononuclear nonheme iron(IV)-oxo oxidant with a 2 His/ 1Asp structural motif analogous to aketoglutarate dependent dioxygenases are presented. The calculations show that these oxidants are very efficient and able to hydroxylate strong C-H bonds,... 

In the present work, nanostructured aluminum titanate (Al2TiO5 or AT) was synthesized by the sol-gel method and potential effects of mechanical strain on its phase analysis, morphology, and thermal stability were investigated in some details for the first time, because the thermal instability of AT is beneficial to the fabrication of in-situ aluminum matrix composites. To characterize the particle distribution, microstructure and thermal durability of AT after the strain induction, field-emission scanning electron microscope (FE-SEM), differential scanning calorimetry (DSC), and x-ray diffraction analysis (XRD) were utilized. The experimental results showed that a 3-h ball milling process... 

Molecules acting as antioxidants capable of scavenging reactive oxygen species (ROS) are of upmost importance in the living cell. Thymol derivatives exhibit various antioxidant activities and potential health benefits. Exploration of structure-radical scavenging activity (SAR) was approached with a wide range of thymol derivatives. To accomplish this task, the DPPH experimental assay along with quantum-chemical calculations were also employed for these compounds. By comparing the structural properties of the derivatives of interest, their antioxidant activity was explained by the formation of an intramolecular hydrogen bond and the presence of unsaturated double bond (–CHdouble bond; length... 

Bromophenols are known as antioxidant radical scavengers for some biomolecules such as those in marine red alga. Full understanding of the role played by bromophenols requires detailed knowledge of the radical scavenging activities in probable pathways, a focus of ongoing research. To gain detailed insight into two suggested pathways, H-atom transfer and electron transfer, theoretical studies employing first principle quantum mechanical calculations have been carried out on selected bromophenols. Detailed investigation of the aforementioned routes revealed that upon H-atom abstraction or the electron transfer process, bromophenols cause an increase in radical species in which the unpaired... 

In this paper, a comprehensive study was conducted on the application of various MeAl2O4 spinels (Me = Fe, Co, Ni, Cu, Zn, Mg) as the catalyst support for the preparation of nickel-based catalysts in the combined dry reforming and partial oxidation. These supports were synthesized by a novel facile sol-gel method using propylene oxide as the gelation agent and nickel was deposited on these supports by the deposition-precipitation method. The prepared samples were characterized by N2 adsorption/desorption, XRD, TPR, TPO, CO2-TPD, SEM, and TEM techniques. In addition, the temperature-programmed methane dissociation (TPMD) was performed to evaluate the effect of nickel-support interaction on... 

Three dimensional calculations of electronic dynamics of CH4 in a strong laser field are presented with time-dependent density-functional theory. Time evolution of dipole moment and electron localization function is presented. The dependence of dissociation rate on the laser characters is shown and optimal effective parameters are evaluated. The optimum field leads to 76% dissociation probability for Gaussian envelope and 40 fs (FWHM) at 10 16 W cm-2. The dissociation probability is calculated by optimum convolution of dual short pulses. By combining of field assisted dissociation process and Ehrenfest molecular dynamics, time variation of bond length, velocity and orientation effect are... 

The optimum convolution of dual short pulse for producing the maximum wakefield and the highest dissociation probability of CH4 has been investigated. By using three fundamental shapes of pulses though four different arrangements, the generated wake are considered in plasma. It is found that when the first and second pulses were rectangular-triangular and sinusoidal pulse shapes, respectively, the resultant wakefield amplitude is the highest. This effect opens up a new novel way by pulse shaping mechanism in the photo dissociation dynamics of molecules and controlling of chemical reactions in the desired channels by short pulse intense lasers for reducing the computation time of genetic... 

The effect of strong femto-second laser pulses on the dissociation probability of methane has been investigated analytically in various arrangements. The ellipticity dependence of the dissociation probability at intensities from 1014 W cm-2 to 1016 W cm-2 for Ti:Sapphire laser is presented. A reliable calculation of the dissociation probability based on 3D time-dependent Schrodinger equation with an improved model of time-dependent density-functional theory is presented. These calculations are carried out for three different cases of elliptically polarized laser pulse, optimum convolution of dual short pulses, and two-color mixed nonresonant laser pulses. It is found that the rescattering... 

The multielectron dissociative ionization of CH4 and CH2O molecules has been investigated using optimum convolution of different dual tailored short laser pulses. Based on three dimensional molecular dynamics simulations and TDDFT approach, the dissociation probability is enhanced by designing the dual chirped-chirped laser pulses and chirped-ordinary laser pulses for formaldehyde molecule. However, it is interesting to notice that the sensitivity of enhanced dissociation probability into different tailored laser pulses is not significant for methane molecule. In this presented modifications, time variation of bond length, velocity, time dependent electron localization function and evolution... 

Three dimensional calculation of control dynamics for finding the optimized laser filed is formulated using an iterative method and time-dependent density functional approach. An appropriate laser pulse is designed to control the desired products in the dissociation of methane molecule. The tailored laser pulse profile, eigenstate distributions and evolution of the efficient occupation numbers are predicted and exact energy levels of this five-atomic molecule is obtained. Dissociation rates of up to 78%, 80%, 90%, and 82% for CH2 +, CH+, C+ and C++ are achieved. Based on the present approach one can reduce the controlling costs. © 2016 Elsevier B.V  

A novel kappa-carrageenan (κC)-based superabsorbing hydrogel was synthesized through graft copolymerization of acrylamide (AAm) onto a κC substrate in the presence of a crosslinking agent. The crosslinked κC-poly(AAm) polymer graft was partially hydrolyzed in alkaline medium to yield a superabsorbent resin, H-carragPAM. The resin structure was confirmed using FTIR spectroscopy. The variables of graft copolymerization (monomer, initiator, polysaccharide and crosslinker concentration, reaction temperature and time as well as stirrer speed) that affected on the ultimate water-swelling capacity were optimized. The time-temperature variation of the copolymerization was investigated in terms of... 

Methane reforming by carbon dioxide in pulsed glow discharge at atmospheric pressure is examined. The plasma pulse is compressed to less than 50 ns. This compression enables one to work at higher frequencies, over 3 kHz, without glow-arc transition. The main products of the reaction are synthetic gases (H2, CO) and C2 hydrocarbons. Approximately 42% of plasma energy goes to the chemical dissociation, when the reactant ratio is C O2 C H4 =1. At this point, the energy expense is less than 3.8 eV per converted molecule while reactant conversions are relatively high reaching to 55% (C H4) and 42% (C O2). The reactor energy performance even gets better at higher C O2 C H4 ratios. While energy... 

The efficient production of syngas from a CH4+CO2 mixture in an atmospheric pulsed glow discharge, sustained by corona pre-ionization, has been investigated. The products were mainly syngas (CO, H2) and hydrocarbons up to C4, with acetylene having the highest selectivity. The energy efficiency was within 15-40% for different experimental conditions, which demonstrates a comprehensive improvement relative to the achievements of other types of non-equilibrium plasma. These values are, however, comparable with the efficiencies obtained by gliding arc plasmas but this plasma operates at near room temperature. Furthermore, it has been shown that the energy efficiency is increased by decreasing...