Quantum mechanical studies on the singlet and triplet potential energy surface of the reactions CF3O2 + I,CF3O + OI and CF3 + OIO

The singlet and triplet potential energy surfaces for the reactions CF₃O₂ + I (1), CF₃O + OI (2) and CF₃ + OIO (3) are investigated using ab initio quantum mechanical methods. Four important isomeric energy minima were found, three on the singlet surface, CF₃OOI, CF₃OIO and CF₃IO₂ and one on the triplet surface ³CF₃OIO. CF₂O + FOI are shown to be the most probable products for all reactions, CF₃O +I and CF₃O + O(³P) are possible for reactions (2) and (3) while the reaction pathway leading to CF₃O +OI is also possible for reaction (3).     

PSM studies III. A model of post-stimulatory masking phenomena

The experimental results obtained from a study of post-stimulatory masking phenomena are summarized. Two mechanisms are postulated to explain these results. A model, based on these two mechanisms, is derived, and comprises the input from the auditory senses, on which preliminary decisions and actions are taken, followed by a selective filter and limited capacity channel leading to the higher brain centres which can effect overriding control on the system. This model is used to provide explanations of the experimental results obtained in this study.     

Acoustic wave effects on catalysis: design of surfaces with artificially controllable functions for chemical reactions

The effects of surface acoustic wave (SAW) and resonance oscillation (RO) of bulk acoustic waves on the catalysis of metals were studied in an attempt to design a catalyst surface with artificially controllable functions for chemical reactions. In ethanol decomposition on a thin Cu film catalyst deposited on the propagation path of a shear horizontal leaky SAW, the SAW-on increased the activity for ethylene production remarkably but a little for acetaldehyde production. A poled ferroelectric z-cut LiNbO₃ with a thickness extensional mode RO (TERO) and a x-cut LiNbO₃ with a thickness shear mode RO (TSRO) were employed as a substrate, on which a thin Ag film catalyst was deposited. For ethanol decomposition, TERO increased ethylene production activity and the selectivity for ethylene production from 79 to 96%, whereas TSRO caused little activity enhancement for both ethylene and acetaldehyde production. The combination with the results of laser Doppler measurements showed that the activity enhancement and selectivity changes with SAW and RO of the acoustic waves are associated with dynamic large lattice displacement vertical to the surface.     

Quantum chemical study of mechanisms of dissociation and isomerization reactions in some molecules and radicals of astrophysical significance: Cyanides and related molecules

A theoretical study of the mechanism of photodecomposition in carbonyl cyanide, diethynyl ketone, acetyl cyanide and formyl cyanide has been conducted using density functional and MP2 theories. A complete analysis of the electronic spectra of these molecules in terms of nature, energy and intensity of electronic transitions has been provided by time-dependent density functional theory. Mixing coefficients and main configurations of the electronic states have been used to identify the states leading to the photodecomposition process. While the Rydberg state ¹(n,3s) is involved in the dissociation of formyl cyanide and acetyl cyanide, the π*_CC/π*_CN states are involved in the case of carbonyl cyanide and diethynyl ketone. In all cases, however, stepwise decomposition process is preferred over the concerted reaction process. Based on potential energy curves for bond dissociation and the transition state and IRC studies, it is found that besides the direct dissociation of carbonyl cyanide, a photoisomerization process through a non-planar transition state may also occur resulting in the formation of a stable and planar isomer CNC(O)CN. A complete vibrational analysis of the higher energy isomer has been conducted and several new fundamental bands are predicted. Some of the earlier experimental results on the photodecomposition mechanism and energies of photofragments in carbonyl cyanide and acetyl cyanide have been rationalized.     

Transport theory of deeply inelastic heavy-ion collisions based on a random-matrix model. III. Calculation of cross sections. Comparison with the reaction Ar + Th

The transport equation deduced previously is cast into a form which allows for numerical computation of cross sections. The approximations, especially the moments approach, are exhibited, as are essential points of the numerical procedure. The validity of the Einstein relation is discussed. Doubly differential cross sections for various fragments produced in the reaction ⁴⁰Ar + ²³²Th are calculated and compared with experimental data.     

Stability studies of alprazolam tablets: effects of chemical interactions with some excipients in pharmaceutical solid preparations

An HPLC method was developed to determine the stability of alprazolam (AL) as a pure drug and in monodrug pharmaceutical tablets. The main degradation product of AL tablets was isolated and fully characterized as triazolaminoquinoleine (TAQ). For a quantitative evaluation of the excipient effects in the pharmaceutical formulations, a 2^k fractionated factorial design was applied in the preparation of the different samples. The kinetic of degradation of AL in each formulation was followed by UV spectrophotometry. It was found that excipients like CMC and magnesium stearate favour degradation, while the rate of the reaction is decreased when lactose and starch were used as excipients. A mechanism for the interactions of AL with some excipients is postulated that explains the observed results. Copyright © 2009 John Wiley & Sons, Ltd.     

Flame treatment on plastic: A new surface free energy statistical prediction model and characterization of treated surfaces

Flame treatments on polymeric materials improve surface free energy (SFE) and consequently the wettability and adhesion of coatings, metallizations, varnish and glues. In this paper, using a statistical methodological approach based on DoE technique and multivariate analysis of flame treatment process parameters, a mathematical model of SFE and wettability is obtained.Contact angle experimental technique was applied to measure the improvement of wettability and SFE.In order to study the oxygen diffusion within the polymer, morphological variation and change of its structure, analyses of treated surface sample were carried out on micro and nano scales.X-ray photoelectron spectroscopy analysis, performed before and after flame treatment, showed the O-radical group improvement on a polymeric surface.Focused ion beam and transmission electron microscopy technology were used to determine the exact thickness of the polymeric material influenced by flame treatment, identifying a composite change on nano scale and a porosity change on microscale.     

The interaction of hydrogen with stepped surfaces of copper: A pairwise-additive model

A pairwise-additive model, with Morse functions as the two-body potentials, has been employed to study stepped surfaces of copper. In general, the hydrogen-atom-copper bond energy is increased when one or more copper atoms are added to the surface at sites different from that which the hydrogen atom is approaching. Approaches of the hydrogen atom to a step face produced hydrogen-copper binding energies larger than those found in the absence of the step. Variations in these general observations are noted for alterations of the approach site environment.     

Help: A model for evaluating the feasibility of using various chemical reaction systems as electronic lasers

An analytical model for estimating the minimum requirements of a chemically pumped electronic laser is developed. From a knowledge of the basic spectroscopic and thermodynamic properties of a particular reaction, the model can quickly classify the system in accordance with the feasibility of generating stimulated emission at different possible wavelengths. Sample calculations of the reactions of barium atoms with nitrous oxide and nitrogen dioxide indicate that the model is sufficiently sensitive to distinguish between very similar systems and, therefore, should be useful in providing classification criteria in the search for a chemically pumped electronic laser.     

Dynamics of the O(1D) D2 reaction: A comparison between crossed molecular beam experiments and quasiclassical trajectory calculations on the lowest three potential energy surfaces

This paper describes crossed beam experiments and quasiclassical trajectory (QCT) calculations for the 'insertion' reaction O(1D)+D2 at a collision energy (Ec=25.9 kJ mol-1) much higher than the calculated barrier (～8.4 kJ mol-1) for the competitive 'abstraction' mechanism, which takes place along the excited state potential energy surfaces (PES). Adiabatic QCT calculations were carried out on the ground 11A' and first excited 11A'' PESs developed by Dobbyn and Knowles. Non-adiabatic contributions from the excited 21A' PES to the reaction were considered by means of a trajectory surface hopping method. QCT calculations were also performed at Ec=22.2 kJ mol-1 to compare with previous experimental results. Excellent agreement was found between experiment and QCT predictions at Ec=22.2 kJ mol-1, while at the higher Ec of 25.9 kJ mol-1 only a qualitative agreement was noted. In all cases, the comparison was significantly improved with respect to QCT calculations on a previous version of the ground state PES.     

Valence shell photoionization spectra of some substituted hydroxy-acetylenes. A tentative correlation with their cyclotrimerization reactions

He(I) photoelectron spectra of a series of oxyacetylenes have been studied. The π_CC and oxygen “lone pair” IE's have been tentatively related to the chemical behaviour of these compounds. CNDO/2 calculations have been carried out on the three simplest molecules of the series.     

Insights into the C(4)H(8)(+.) potential energy surface: fourier transform ion cyclotron resonance studies of ion-molecule reactions of D-labeled partners

Reactions of [ethylene](+.) with ethylene and of [acetylene](+.) with ethane were studied by Fourier transform ion cyclotron resonance spectrometry using labeled reactants. The results confirm and clarify the different steps of the mechanism proposed previously and elaborated with other methods. The [[acetylene](+.), ethane] system can either dissociate to give the ethyl cation product, or isomerize into [[ethylene](+.), ethylene]. The latter system can either dissociate to yield ionized ethylene or convert into ionized but-2-ene, which undergoes a complete H-exchange prior to dissociation, leading to methyl radical, hydrogen radical and ethylene losses. The transfers of labeled atoms and the existence of H-exchange prior to formation of the products were used as a probe to check the different steps of the mechanism. The influence of the initial energy of the system on the reaction pathway is discussed. Copyright 1999 John Wiley & Sons, Ltd.     

Study of low energy noble gas ion reflection from monocrystalline surfaces; influence of thermal vibrations of the surface atoms: III. A qualitative comparison of experimental and calculational results

The validity of explaining the thermal effects using the chain model approach is investigated. For this purpose a copper (100) surface was bombarded along a 〈100〉 and a 〈110〉 direction, with low energetic noble gas ions. The comparison is troubled by charge exchange effects, which affect strongly the shape of the experimental energy distributions. At highej target temperatures the calculated temperature dependences agree with the experimental observations. At target temperatures below about 400 K discrepancies arise, which can be ascribed satisfactorily to the appearance of surface defects. The angular distributions depend strongly on the occurrence of charge exchange processes. They can be corrected for these effects using a model proposed earlier by the authors.     

Surface interactions of Au(I) cyclo-trimer with Au(111) and Al(111) surfaces: A computational study

A plane-wave density functional theory (DFT) study on surface interactions of a cyclo-[Au(μ-Pz)]₃ monolayer (denoted as T), Pz = pyrazolate, with Au(111) and Al(111) surfaces (denoted as M′) has been performed. Structural and electronic properties at the M′–T interfaces are determined from individually optimized structures of M′, T and M′–T. Results show that the gold pyrazolate trimer (T) binds more strongly on the Au(111) surface than on Al(111). Charge redistribution has been observed at both M′–T interfaces, where charge is “pushed” back towards the Au(111) surface from the trimer monolayer in Au(111)–T system, while the opposite happens in the Al(111)–T system where the charge is being pushed toward the trimer monolayer from the Al(111) surface. Considerable changes to the work function of Au(111) and Al(111) surfaces upon the trimer adsorption which arise from monolayer vacuum level shifts and dipole formation at the interfaces are calculated. The interaction between cyclo-[Au(μ-Pz)]₃ with metal surfaces causes band broadening of the gold pyrazolate trimer in M′–T systems. The present study aids better understanding of the role of intermolecular interactions, bond dipoles, energy-level alignment and electronic coupling at the interface of metal electrodes and organometallic semiconductor to help design metal–organic field effect transistors (MOFETs) and other organometallic electronic devices.     

Kinetics of the reaction of oxygen with clean nickel single crystal surfaces: I. Ni(100) surface

The initial stages of the interaction of oxygen gas with a clean Ni (100) surface have been studied by a combination of LEED, AES, work function change and ion bombardment sectioning techniques. The reaction could be divided into three reaction regions: a fast dissociative chemisorption leading to surface structures based on the initial nickel interatomic spacing and resulting in an oxygen coverage of approximately 0.4 monolayers; a rapid oxidation leading to epitaxial NiO, two layers thick ; and a final slow thickening of bulk NiO. The first two regions were dependent only upon oxygen exposure. The third region was observed only at high gas-phase oxygen pressures or very low surface temperatures. Kinetics analyses are developed to explain the rate of oxygen chemisorption and the rate of oxide nucleation and growth.     

A simple model for a symmetrical theory of generalized functions: III. Products of generalized functions

The product and convolution product of all generalized functions is defined. This is applied to obtain the Hilbert transform and the dispersion relations for causal systems.     

A mean-field,effective medium theory of random binary alloys III. The ising model with competing interactions

The Ising model with competing interactions is studied in a mean field effective medium approach. The phase diagram of such model alloys is studied. We conclude that for all ratios of the competing interaction moments, a spin glass phase always exists at low temperatures for certain concentration regimes.