First-principles study of oxygenates on Co surfaces in Fischer-Tropsch synthesis

Extensive density function theory calculations are performed to study the mechanism of the formation of aldehyde and alcohol on Co surfaces in Fischer-Tropsch synthesis, a challenging issue in heterogeneous catalysis. Three possible pathways for the production of formaldehyde and methanol on flat and stepped Co(0001) surfaces are investigated: (i) CO + 4H -> CHO + 3H -> CH2O + 2H -> CH3O + H -> CH3OH; (ii) CO + 4H -> COH + 3H -> CHOH + 2H -> CH2OH + H -> CH3OH; and (iii) the coupling reactions of CH2 + O -> CH2O and CH3 + OH -> CH3OH. It is found that these pathways are generally favored at step sites, and the preferred mechanism is pathway (i) via CHO. Furthermore, the three traditional chain growth mechanisms in Fischer-Tropsch synthesis are semi quantitatively compared and discussed. Our results suggest that the two mechanisms involving oxygenate intermediates (the CO-insertion and hydroxycarbene mechanisms) are less important than the carbene mechanism in the production of long chain hydrocarbons. However, the CO-insertion mechanism may be responsible for the production of long-chain oxygenates.

General trends in CO dissociation on transition metal surfaces

Dissociative adsorption is one of the most important reactions in catalysis. In this communication we propose a model aiming to generalize the important factors that affect dissociation reactions. Specifically, for a dissociation reaction, say AB -->A + B, the model connects the dissociation barrier with the association barrier, the chemisorption energies of A and B at the final state and the bonding energy of AB in the gas phase. To apply this model, we have calculated CO dissociation on Ru(0001), Rh(111), Pd(111) (4d transition metals), Os(0001), Ir(111), and Pt(111) (5d transition metals) using density function theory (DFT). All the barriers are determined. We find that the DFT results can be rationalized within the model. The model can also be used to explain many experimental observations. (C) 2001 American Institute of Physics.

Density functional study of the C atom adsorption on the α-Fe 2O3 (001) surface

The adsorption of C atoms on the α-Fe₂O₃ (001) surface was studied based on density function theory (DFT), in which the exchange-correlation potential was chosen as the PBE (Perdew, Burke and Ernzerhof) generalized gradient approximation (GGA) with a plane wave basis set. Upon the optimization on different adsorption sites with coverage of 1/20 and 1/5 ML, it was found that the adsorption of C atoms on the α-Fe ₂O₃ (001) surface was chemical adsorption. The coverage can affect the adsorption behavior greatly. Under low coverage, the most stable adsorption geometry lied on the bridged site with the adsorption energy of about 3.22 eV; however, under high coverage, it located at the top site with the energy change of 8.79 eV. Strong chemical reaction has occurred between the C and O atoms at this site. The density of states and population analysis showed that the s, p orbitals of C and p orbital of O give the most contribution to the adsorption bonding. During the adsorption process, O atom shares the electrons with C, and C can only affect the outermost and subsurface layers of α-Fe₂O₃; the third layer can not be affected obviously. Copyright © 2008 Chinese Journal of Structural Chemistry.

Strong second harmonic generation in SiC, ZnO, GaN two-dimensional hexagonal crystals from first-principles many-body calculations

The second harmonic generation (SHG) intensity spectrum of SiC, ZnO, GaN two-dimensional hexagonal crystals is calculated by using a real-time first-principles approach based on Green's function theory [Attaccalite et al., Phys. Rev. B: Condens. Matter Mater. Phys. 2013 88, 235113]. This approach allows one to go beyond the independent particle description used in standard first-principles nonlinear optics calculations by including quasiparticle corrections (by means of the GW approximation), crystal local field effects and excitonic effects. Our results show that the SHG spectra obtained using the latter approach differ significantly from their independent particle counterparts. In particular they show strong excitonic resonances at which the SHG intensity is about two times stronger than within the independent particle approximation. All the systems studied (whose stabilities have been predicted theoretically) are transparent and at the same time exhibit a remarkable SHG intensity in the range of frequencies at which Ti:sapphire and Nd:YAG lasers operate; thus they can be of interest for nanoscale nonlinear frequency conversion devices. Specifically the SHG intensity at 800 nm (1.55 eV) ranges from about 40-80 pm V(-1) in ZnO and GaN to 0.6 nm V(-1) in SiC. The latter value in particular is 1 order of magnitude larger than values in standard nonlinear crystals.

Studies in the geometry of the discrete plane

This thesis is an attempt to initiate the development of a discrete geometry of the discrete plane H = {(qmxo,qnyo); m,n e Z - the set of integers}, where q s (0,1) is fixed and (xO,yO) is a fixed point in the first quadrant of the complex plane, xo,y0 ¢ 0. The discrete plane was first considered by Harman in 1972, to evolve a discrete analytic function theory for geometric difference functions. We shall mention briefly, through various sections, the principle of discretization, an outline of discrete a alytic function theory, the concept of geometry of space and also summary of work done in this thesis

A New Approach to the Prediction of Partition Coefficients in Water/Organic Interfaces

In the present work, a new approach for the determination of the partition coefficient in different interfaces based on the density function theory is proposed. Our results for log P(ow) considering a n-octanol/water interface for a large super cell for acetone -0.30 (-0.24) and methane 0.95 (0.78) are comparable with the experimental data given in parenthesis. We believe that these differences are mainly related to the absence of van der Walls interactions and the limited number of molecules considered in the super cell. The numerical deviations are smaller than that observed for interpolation based tools. As the proposed model is parameter free, it is not limited to the n-octanol/water interface.

The effects of dye dopants on the conductivity and optical absorption properties of polypyrrole

Ten anionic compounds, including four acidic dyes, were used to dope polypyrrole powder. The effects of the dopants on density, optical absorption and conductivity of the polypyrroles were studied. The presence of the dopant in the conducting polymer matrix was verified by ATR-FTIR spectroscopy. Density function theory (DFT) simulation was used to understand the effect of the dopants on the solid structure, optical absorption and energy band structures. Anthraquinone-2-sulfonic acid-doped polypyrrole yielded the highest conductivity. The dye-doped polypyrrole showed an enhancement in its UV–vis optical absorption.

Definite integrals and operational methods

An operational method, already employed to formulate a generalization of the Ramanujan master theorem, is applied to the evaluation of integrals of various types. This technique provides a very flexible and powerful tool yielding new results encompassing different aspects of the special function theory. Crown Copyright (C) 2012 Published by Elsevier Inc. All rights reserved.

Studies of pure rotational spectra of isolated molecules and molecular adducts using pulsed jet Fourier transform microwave (PJ-FTM) spectroscopy

This thesis focuses on studying molecular structure and internal dynamics by using pulsed jet Fourier transform microwave (PJ-FTMW) spectroscopy combined with theoretical calculations. Several kinds of interesting chemical problems are investigated by analyzing the MW spectra of the corresponding molecular systems. First, the general aspects of rotational spectroscopy are summarized, and then the basic theory on molecular rotation and experimental method are described briefly. ab initio and density function theory (DFT) calculations that used in this thesis to assist the assignment of rotational spectrum are also included. From chapter 3 to chapter 8, several molecular systems concerning different kind of general chemical problems are presented. In chapter 3, the conformation and internal motions of dimethyl sulfate are reported. The internal rotations of the two methyl groups split each rotational transition into several components line, allowing for the determination of accurate values of the V3 barrier height to internal rotation and of the orientation of the methyl groups with respect to the principal axis system. In chapter 4 and 5, the results concerning two kinds of carboxylic acid bi-molecules, formed via two strong hydrogen bonds, are presented. This kind of adduct is interesting also because a double proton transfer can easily take place, connecting either two equivalent or two non-equivalent molecular conformations. Chapter 6 concerns a medium strong hydrogen bonded molecular complex of alcohol with ether. The dimer of ethanol-dimethylether was chosen as the model system for this purpose. Chapter 7 focuses on weak halogen…H hydrogen bond interaction. The nature of O-H…F and C-H…Cl interaction has been discussed through analyzing the rotational spectra of CH3CHClF/H2O. In chapter 8, two molecular complexes concerning the halogen bond interaction are presented.

Does upward social mobility increase life satisfaction? A longitudinal analysis using British and Swiss panel data

A main assumption of social production function theory is that status is a major determinant of subjective well-being (SWB). From the perspective of the dissociative hypothesis, however, upward social mobility may be linked to identity problems, distress, and reduced levels of SWB because upwardly mobile people lose their ties to their class of origin. In this paper, we examine whether or not one of these arguments holds. We employ the United Kingdom and Switzerland as case studies because both are linked to distinct notions regarding social inequality and upward mobility. Longitudinal multilevel analyses based on panel data (UK: BHPS, Switzerland: SHP) allow us to reconstruct individual trajectories of life satisfaction (as a cognitive component of SWB) along with events of intragenerational and intergenerational upward mobility—taking into account previous levels of life satisfaction, dynamic class membership, and well-studied determinants of SWB. Our results show some evidence for effects of social class and social mobility on well-being in the UK sample, while there are no such effects in the Swiss sample. The UK findings support the idea of dissociative effects in terms of a negative effect of intergenerational upward mobility on SWB.

Modelos determinístico y probabilístico para la estimación de la carga de nitratos en una cuenca rural

En este trabajo se desarrolló un modelo probabilístico que utiliza la teoría de la función de densidad de probabilidades derivada para estimar la carga media anual de nitratos transportada por el escurrimiento superficial, utilizando una relación funcional entre el escurrimiento y la carga de nitratos. El modelo determinístico hidrológico y de calidad de agua denominado Simulator for Water Resources in Rural Basins - Water Quality (SWRRB-WQ) fue utilizado para estimar la carga de nitratos en el escurrimiento superficial. Este modelo emplea como variable de entrada la precipitación diaria observada en la Estación del Aeropuerto de Olavarría durante el período 1988 a 2002. Para la calibración del modelo se aplicó una nueva metodología que estima la incertidumbre en los valores observados. Ambos modelos probabilístico y determinístico se aplican en una subcuenca rural del arroyo Tapalqué (provincia de Buenos Aires, Argentina) y finalmente se comparan los valores de la carga de nitratos estimados con los dos modelos con las observaciones realizadas en la sección del arroyo motivo de este estudio. Los resultados muestran que la carga media de nitratos obtenida con el modelo probabilístico es del mismo orden de magnitud que los valores medios observados y estimados con el modelo hidrológico y de calidad de agua SWRRB-WQ.

Three-dimensional modeling of and ligand docking to vitamin D receptor ligand binding domain

The ligand binding domain of the human vitamin D receptor (VDR) was modeled based on the crystal structure of the retinoic acid receptor. The ligand binding pocket of our VDR model is spacious at the helix 11 site and confined at the β-turn site. The ligand 1α,25-dihydroxyvitamin D3 was assumed to be anchored in the ligand binding pocket with its side chain heading to helix 11 (site 2) and the A-ring toward the β-turn (site 1). Three residues forming hydrogen bonds with the functionally important 1α- and 25-hydroxyl groups of 1α,25-dihydroxyvitamin D3 were identified and confirmed by mutational analysis: the 1α-hydroxyl group is forming pincer-type hydrogen bonds with S237 and R274 and the 25-hydroxyl group is interacting with H397. Docking potential for various ligands to the VDR model was examined, and the results are in good agreement with our previous three-dimensional structure-function theory.

Reflections on the role and design of online dictionaries for specialised translation

This article is an updated and modified version of a Spanish article published in MonTi 6 (cf. Tarp 2014a). It deals with specialised translation dictionaries. Based on the principles of the function theory, it analyses the different phases and sub-phases of the translation process from a lexicographical perspective and shows that a translation dictionary should be much more than a mere bilingual dictionary if it really pretends to meet its users’ complex needs. Thereafter, it presents a global concept of a translation dictionary which includes various mono- and bilingual components in both language directions. Finally, the article discusses, by means of two concrete online projects, how this concept can be applied on the Internet in order to develop high-quality translation dictionaries with quick access to data that are still more adapted to the needs of each translator.