Theoretical study for the interlamellar aminoalcohol functionalization of kaolinite
Energy Technology Data Exchange (ETDEWEB)
Hou, Xin-Juan [Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Li, Huiquan, E-mail: hqli@home.ipe.ac.cn [Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China); Liu, Qinfu; Cheng, Hongfei [School of Geoscience and Surveying Engineering, China University of Mining and Technology, Beijing 100083 (China); He, Peng; Li, Shaopeng [Key Laboratory of Green Process and Engineering, National Engineering Laboratory for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190 (China)
2015-08-30
Graphical abstract: - Highlights: • The results indicated that aminoalcohols exist with a mixing of intercalation and grafting. • Aminoalcohols can form strong hydrogen bonds with Al octahedral sheet. • The interaction between aminoalcohols and Si tetrahedral sheet are mainly attributed by vdW force. • Aminoalcohols grafting or intercalating on kaolinite have strong reactivity as electron donors. - Abstract: Fundamental problems related to aminoalcohols intercalating on kaolinite were investigated by using density functional theory method. This study examines the adsorption modes of diethanolamine and triethanolamine on kaolinite, the role of hydrogen bonds and van der Waals (vdW) forces between aminoalcohols and interlayer of kaolinite, and the change of molecular orbital occupancies of functionalized kaolinite. Results show that functionalized kaolinite is physically intercalated and covalently grafted by aminoalcohols. Non-covalent interaction analysis provides a visualized description that intercalated aminoalcohols form strong hydrogen bonds with Al octahedral sheet, and the interaction between aminoalcohols and Si tetrahedral sheet is mainly attributed to weak vdW force. The analysis of molecular orbital occupancies for kaolinite complex showed that the functionalized kaolinite has strong chemical reactivity as electron donors on the sites of grafted or intercalated aminoalcohols for further chemical reaction with other materials.
Chemical functionalization of graphene via aryne cycloaddition: a theoretical study.
Zhao, Jing-xiang; Wang, Hong-xia; Gao, Bo; Wang, Xiao-guang; Cai, Qing-hai; Wang, Xuan-zhang
2012-06-01
Chemical functionalization of graphene provides a promising route to improve its solubility in water and organic solvents as well as modify its electronic properties, thus significantly expanding its potential applications. In this article, by using density functional theory (DFT) methods, we have studied the effects of the chemical functionalization of graphenes via aryne cycloaddition on its properties. We found that the adsorption of an isolated aryne group on the graphene sheet is very weak with the adsorption energy of -0.204 eV, even though two new single C-C interactions are formed between the aryne group and the graphene. However, the interaction of graphene with the aryne group can be greatly strengthened by (i) substituting the H-atoms in aryne group with F-, Cl-, -NO(2) (electron-withdrawing capability), or CH(3)-group (electron-donating capability), and (ii) increasing the coverage of the adsorbed aryne groups on the graphene sheet. As expected, the strongest bonding is found on the graphene edges, in which the adsorbed aryne groups prefer to be far away from each other. Interestingly, chemical functionalization with aryne groups leads to an opening of the band gap of graphene, which is dependent on the coverage of the adsorbed aryne groups. The present work provides an insight into the modifications of graphene with aryne groups in experiment.
Graphene functionalization by single atoms doping - a theoretical study
Natan, Amir; Segev, Elad; Hersam, Mark; Seideman, Tamar
2014-03-01
We present first principles results and analysis for the electronic structure of chemically modified graphene. We analyze the cases of fluorine adsorption and nitrogen substitution and show that a simple analytical model can describe the doping level as a function of dopant concentration for both cases. We show the relationship between different physical parameters and the electronic band structure of the modified material and its doping level. Finally, we discuss the possible effects of substrate and of different dopant patterns on the band structure and possible applications. amirnatan@post.tau.ac.il
Theoretical study of the dipole moment function of OH(X2Pi)
Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Taylor, Peter R.
1989-01-01
A theoretical study of the sensitivity of the dipole moment function (DMF) of the X2Pi ground state of OH to basis-set saturation and to refinements in the correlation treatment is presented. Emphasis is placed on determining the slope of the DMF at r(e) and the r value at which the maximum occurs. Consideration is given to the effect of oxygen polarization functions up through h type, expansion of the active orbital space to include the O 3d-delta orbital, the effect of higher excitations using the averaged coupled-pair functional method, and the effect of evaluating the dipole moment as an energy derivative rather than as an expectation value. The theoretical DMFs obtained here, which should be the most accurate to date, differ markedly from an empirical DMF of Turnbull and Lowe that is based on experimentally derived intensity ratios. The theoretical DMFs agree better with a recently published DMF of Nelson et al., but suggest that this empirical DMF is also inaccurate for r greater than 2.3 a0.
Molecular orbital ab initio and density functional theoretical study on reaction between PH2 and NO
Institute of Scientific and Technical Information of China (English)
HU; Zhengfa(胡正发); WANG; Zhenya(王振亚); LI; Haiyang(李海洋); ZHOU; Shikang(周士康)
2002-01-01
The theoretical study of reaction between PH2 and NO on the ground state potential energy surface is reported by using molecular orbital ab initio calculation and density function theory (DFT). Equilibrium structural parameters, harmonic vibrational frequencies, total energies and zero point energies of all species during reaction are computed by HF, MP2 (full) and B3LYP theory levels with the medium basis set 6-31G*. Theoretical results indicate that intermediate IM1(H2PNO) is firstly formed by overcoming a small energy barrier TS1, and then two four-membered ring transient states TS2 and TS5, with energy barriers 103.3 and 102.6 kJ/mol respectively,then H-migration and isomerization are completed and the products PN and H2O are formed. The reaction is exothermic one with -189.6 k J/mol released.
Energy Technology Data Exchange (ETDEWEB)
Kilina, Svetlana [Los Alamos National Laboratory; Tretiak, Sergei [Los Alamos National Laboratory; Sykora, Milan [Los Alamos National Laboratory; Albert, Victor [UNIV OF FLORIDA; Badaeva, Ekaterina [UNIV OF WASHINGTON; Koposov, Alexey [UNIV OF WASHINGTON
2008-01-01
New photovoltaic and photocatalysis applications have been recently proposed based on the hybrid Ru(II)-bipyridine-complex/semiconductor quantum dot systems. In order to attach the Ru(II) complex to the surface of a semiconductor, a linking bridge -- a carboxyl group -- needs to be added to one or two of the 2,2'-bipyridine (bpy) ligands. Such changes in the ligand structure affect electronic and optical properties and, consequently, the charge transfer reactivity of Ru(II)-systems. In this study, we analyze the effects brought by functionalization of bipyridine ligands with the methyl, carboxyl, and carboxilate groups on the electronic structure and optical response of the [Ru(bpy){sub 3}]{sup 2+} complex. First principle calculations based on density functional theory (DFT) and time dependent DFT (TDDFT) are used to simulate the ground and excited-state properties, respectively, of functionalized Ru-complexes in the gas phase and acetonitrile solution. In addition, an effective Frenkel exciton model is used to explain the optical activity and splitting patterns of the low-energy excited states in all molecules. All theoretical results nicely complement and allow for detailed interpretation of experimental absorption spectra of Ru-complexes that have been done in parallel with our theoretical investigations. We found that the carboxyl group breaks the degeneracy of two low-energy optically bright excited states and red-shifts the absorption spectrum, while leaves ionization and affinity energies of complexes almost unchanged. Experimental studies show that deprotonation of the carboxyl group in the Ru-complexes results in a slight blue shift and decrease of oscillator strengths of the low energy absorption peaks. Comparison of experimental and theoretical linear response spectra of deprotonated complexes demonstrate strong agreement if the theoretical calculations are performed with the addition of a dielectric continuum model. A polar solvent is found to
Hash Functions and Information Theoretic Security
Bagheri, Nasour; Knudsen, Lars R.; Naderi, Majid; Thomsen, Søren S.
Information theoretic security is an important security notion in cryptography as it provides a true lower bound for attack complexities. However, in practice attacks often have a higher cost than the information theoretic bound. In this paper we study the relationship between information theoretic attack costs and real costs. We show that in the information theoretic model, many well-known and commonly used hash functions such as MD5 and SHA-256 fail to be preimage resistant.
Hash functions and information theoretic security
DEFF Research Database (Denmark)
Bagheri, Nasoor; Knudsen, Lars Ramkilde; Naderi, Majid;
2009-01-01
Information theoretic security is an important security notion in cryptography as it provides a true lower bound for attack complexities. However, in practice attacks often have a higher cost than the information theoretic bound. In this paper we study the relationship between information theoretic...... attack costs and real costs. We show that in the information theoretic model, many well-known and commonly used hash functions such as MD5 and SHA-256 fail to be preimage resistant....
Energy Technology Data Exchange (ETDEWEB)
Ebata, Takayuki; Kusaka, Ryoji [Department of Chemistry, Graduate School of Science, Hiroshima University, Kagamiyama 1-3-1, Higashi-Hiroshima, 739-8526 (Japan); Xantheas, Sotiris S. [Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, 902 Battelle Boulevard, P.O. Box 999, MS K1-83, Richland, WA 99352 (United States)
2015-01-22
Extensive laser spectroscopic and theoretical studies have been recently carried out with the aim to reveal the structure and dynamics of encapsulation complexes in the gas phase. The characteristics of the encapsulation complexes are governed by the fact that (i) most of the host molecules are flexible and (ii) the complexes form high dimensional structures by using weak non-covalent interactions. These characteristics result in the possibility of the coexistence of many conformers in close energetic proximity. The combination of supersonic jet/laser spectroscopy and high level quantum chemical calculations is essential in tackling these challenging problems. In this report we describe our recent studies on the structures and dynamics of the encapsulation complexes formed by calix[4]arene (C4A), dibenzo-18-crown-6-ether (DB18C6), and benzo-18-crown-6-ether (B18C6) 'hosts' interacting with N{sub 2}, acetylene, water, and ammonia 'guest' molecules. The gaseous host-guest complexes are generated under jet-cooled conditions. We apply various laser spectroscopic methods to obtain the conformer- and isomer-specified electronic and IR spectra. The experimental results are complemented with quantum chemical calculations ranging from density functional theory to high level first principles calculations at the MP2 and CCSD(T) levels of theory. We discuss the possible conformations of the bare host molecules, the structural changes they undergo upon complexation, and the key interactions that are responsible in stabilizing the specific complexes.
Band gap engineering in silicene: A theoretical study of density functional tight-binding theory
Zaminpayma, Esmaeil; Nayebi, Payman
2016-10-01
In this work, we performed first principles calculations based on self-consistent charge density functional tight-binding to investigate different mechanisms of band gap tuning of silicene. We optimized structures of silicene sheet, functionalized silicene with H, CH3 and F groups and nanoribbons with the edge of zigzag and armchair. Then we calculated electronic properties of silicene, functionalized silicene under uniaxial elastic strain, silicene nanoribbons and silicene under external electrical fields. It is found that the bond length and buckling value for relaxed silicene is agreeable with experimental and other theoretical values. Our results show that the band gap opens by functionalization of silicene. Also, we found that the direct band gap at K point for silicene changed to the direct band gap at the gamma point. Also, the functionalized silicene band gap decrease with increasing of the strain. For all sizes of the zigzag silicene nanoribbons, the band gap is near zero, while an oscillating decay occurs for the band gap of the armchair nanoribbons with increasing the nanoribbons width. At finally, it can be seen that the external electric field can open the band gap of silicene. We found that by increasing the electric field magnitude the band gap increases.
Wu, Zemin; Rong, Chunying; Lu, Tian; Ayers, Paul W; Liu, Shubin
2015-10-28
As a continuation of our recent efforts to quantify chemical reactivity with quantities from the information-theoretic approach within the framework of density functional reactivity theory, the effectiveness of applying these quantities to quantify electrophilicity for the bimolecular nucleophilic substitution (SN2) reactions in both gas phase and aqueous solvent is presented in this work. We examined a total of 21 self-exchange SN2 reactions for the compound with the general chemical formula of R1R2R3C-F, where R1, R2, and R3 represent substituting alkyl groups such as -H, -CH3, -C2H5, -C3H7, and -C4H9 in both gas and solvent phases. Our findings confirm that scaling properties for information-theoretic quantities found elsewhere are still valid. It has also been verified that the barrier height has the strongest correlation with the electrostatic interaction, but the contributions from the exchange-correlation and steric effects, though less significant, are indispensable. We additionally unveiled that the barrier height of these SN2 reactions can reliably be predicted not only by the Hirshfeld charge and information gain at the regioselective carbon atom, as previously reported by us for other systems, but also by other information-theoretic descriptors such as Shannon entropy, Fisher information, and Ghosh-Berkowitz-Parr entropy on the same atom. These new findings provide further insights for the better understanding of the factors impacting the chemical reactivity of this vastly important category of chemical transformations.
Ben Salah, Issam; Njeh, Anouar; Ben Ghozlen, Mohamed Hédi
2012-02-01
An exact approach is used to investigate Rayleigh waves in a functionally graded piezoelectric material (FGPM) layer bonded to a semi infinite homogenous solid. The piezoelectric material is polarized when the six fold symmetry axis is put along the propagation direction x(1). The FGPM character imposes that the material properties change gradually with the thickness of the layer. Contrary to the analytical approach, the adopted numerical methods, including the ordinary differential equation (ODE) and the stiffness matrix method (SMM), treat separately the electrical and mechanical gradients. The influences of graded variations applied to FGPM film coefficients on the dispersion curves of Rayleigh waves are discussed. The effects of gradient coefficients on electromechanical coupling factor, displacement fields, stress distributions and electrical potential, are reported. The obtained deviations in comparison with the ungraded homogenous film are plotted with respect to the dimensionless wavenumber. Opposite effects are observed on the coupling factor when graded variations are applied separately. A particular attention has been devoted to the maximum of the coupling factor and it dependence on the stratification rate and the gradient coefficient. This work provides with a theoretical foundation for the design and practical applications of SAW devices with high performance.
Theoretical studies of the work functions of Pd-based bimetallic surfaces
Energy Technology Data Exchange (ETDEWEB)
Ding, Zhao-Bin; Wu, Feng; Wang, Yue-Chao; Jiang, Hong, E-mail: jianghchem@pku.edu.cn [Beijing National Laboratory of Molecular Sciences, State Key Laboratory of Rare Earth Materials Chemistry and Applications, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 (China)
2015-06-07
Work functions of Pd-based bimetallic surfaces, including mainly M/Pd(111), Pd/M, and Pd/M/Pd(111) (M = 4d transition metals, Cu, Au, and Pt), are studied using density functional theory. We find that the work function of these bimetallic surfaces is significantly different from that of parent metals. Careful analysis based on Bader charges and electron density difference indicates that the variation of the work function in bimetallic surfaces can be mainly attributed to two factors: (1) charge transfer between the two different metals as a result of their different intrinsic electronegativity, and (2) the charge redistribution induced by chemical bonding between the top two layers. The first factor can be related to the contact potential, i.e., the work function difference between two metals in direct contact, and the second factor can be well characterized by the change in the charge spilling out into vacuum. We also find that the variation in the work functions of Pd/M/Pd(111) surfaces correlates very well with the variation of the d-band center of the surface Pd atom. The findings in this work can be used to provide general guidelines to design new bimetallic surfaces with desired electronic properties.
Theoretical study of functionalized single-walled carbon nanotube (5, 5 with Mitoxantrone drug
Directory of Open Access Journals (Sweden)
F. Shojaie
2016-04-01
Full Text Available Objective(s: First principles calculations were performed to study four multiple sclerosis drugs namely, Ampyra, Fingolimod, Mitoxantrone and Eliprodil in gas and liquid phases using Density Functional Theory (DFT. Computational chemistry simulations were carried out to compare calculated quantum chemical parameters for Ampyra, Fingolimod, Mitoxantrone and Eliprodil. Materials and Methods: All calculations were performed using DMol3 code which is based on DFT. The Double Numerical basis set with Polarization functions (DNP was used.Results: Mitoxantrone has highest HOMO energy, global softness, solvation energy and molecular mass and lowest LUMO energy, energy gap, global hardness and total energy in comparison to Ampyra, Fingolimod and Eliprodil in gas and solvent phases. Calculations were carried out to study the interaction of covalently binding Mitoxantrone to functionalized carbon nanotube. The Mitoxantrone local reactivity was studied through the Fukui indices in order to predict both the reactive centers and the possible sites of nucleophilic and electrophilic attacks. The Mitoxantrone binding energy is calculated to be 6.507 eV in gas phase and -9.943 eV in solvent phase that is a decrease in BE as the drug phase changes from gas to liquid.Conclusion: The simulation results show Mitoxantrone is quite a reactive drug. The quantum chemical parameters of pristine nanotube and f-SWNT-Mitoxantrone showed that reactivity of f-SWNT-Mitoxantrone increased in comparison to pristine nanotube in both phases.
Understanding the bonding nature of uranyl ion and functionalized graphene: a theoretical study.
Wu, Qun-Yan; Lan, Jian-Hui; Wang, Cong-Zhi; Xiao, Cheng-Liang; Zhao, Yu-Liang; Wei, Yue-Zhou; Chai, Zhi-Fang; Shi, Wei-Qun
2014-03-20
Studying the bonding nature of uranyl ion and graphene oxide (GO) is very important for understanding the mechanism of the removal of uranium from radioactive wastewater with GO-based materials. We have optimized 22 complexes between uranyl ion and GO applying density functional theory (DFT) combined with quasi-relativistic small-core pseudopotentials. The studied oxygen-containing functional groups include hydroxyl, carboxyl, amido, and dimethylformamide. It is observed that the distances between uranium atoms and oxygen atoms of GO (U-OG) are shorter in the anionic GO complexes (uranyl/GO(-/2-)) compared to the neutral GO ones (uranyl/GO). The formation of hydrogen bonds in the uranyl/GO(-/2-) complexes can enhance the binding ability of anionic GO toward uranyl ions. Furthermore, the thermodynamic calculations show that the changes of the Gibbs free energies in solution are relatively more negative for complexation reactions concerning the hydroxyl and carboxyl functionalized anionic GO complexes. Therefore, both the geometries and thermodynamic energies indicate that the binding abilities of uranyl ions toward GO modified by hydroxyl and carboxyl groups are much stronger compared to those by amido and dimethylformamide groups. This study can provide insights for designing new nanomaterials that can efficiently remove radionuclides from radioactive wastewater.
Study on the Radius of an Electrical Spherical Micelle:Functional Theoretical Approach
Institute of Scientific and Technical Information of China (English)
WANG,Zheng-Wu(王正武); HUANG,Dong-Yang(黄东阳); YI,Xi-Zhang(易希璋); LI,Gan-Zuo(李干佐)
2004-01-01
For the purpose of eliminating restriction,the Poisson-Boltzmann(PB)equation,which represents the potential of the electrical double layer of spherical micelles,can be solved analytically only under the lower potential condition,a kind of iterative method in functional analysis theory has been used.The radius of the spherical particle can be obtained from the diagram of the second iterative solution of the potential versus the distance from the center of the particle.The influences of the concentration of the ions,the charge number of ions,the aggregation number of the particle,the dielectric constant of solvent and the temperature of system on the radius also have been studied.
A Theoretical Study of Lithium-Doped Gallium Clusters by Density Functional Theory
Şentürk, Şükrü; Ekincioğlu, Yavuz
2012-05-01
The geometrical structures, stabilities, and electronic properties of GanLi (n = 1 - 13) clusters were investigated within the density functional theory (DFT). The impurity lithium atom enhances the stability of GanLi (n = 1 - 13) clusters, especially GanLi (n = 9 - 13) compared to Gan(n = 9 - 14), that is at either apex position or side position. The dissociation energy, second-order energy differences, and the energy gaps between highest occupied and lowest unoccupied molecular orbital (HOMO-LUMO) indicate that the Ga7Li, Ga9Li, and Ga11Li clusters are more stable within the studied cluster range. Moreover, the variation of the average bond length of Ga-Li is due to the surface effect, and the binding strength increases resulting from the increase of charge amount.
Energy Technology Data Exchange (ETDEWEB)
Deng, Shihu; Hou, Gao-Lei; Kong, Xiangyu; Valiev, Marat; Wang, Xue B.
2014-06-30
Aspartate (Asp^{2-}) and Glutamate (Glu^{2-}), two doubly charged conjugate bases of the corresponding amino acids were investigated using low temperature negative ion photoelectron spectroscopy (NIPES) and ab-initio calculations. The effect of amine functionalization was studied by a direct comparison to the parent dicarboxylate species (^{-}CO_{2}–(CH_{2})_{n}–CO_{2}-, DC_{n}^{2-}) -- succinate (DC_{2}^{2-}) and propionate (DC_{3}^{2-}). Experimentally the addition of amine group for n = 2 case (DC_{2}^{2-}, Asp^{2-}) significantly improves the stability of the resultant Asp^{2-} dianionic species, albeit that NIPES shows only a small increase in adiabatic electron detachment energy (ADE) (+0.05eV). In contrast, for n = 3 (DC_{3}^{2-}, Glu^{2-}), much larger ADE increase is observed (+0.15eV). Similar results are obtained through ab-initio calculations. The latter indicates that increased stability of Asp^{2-} can be attributed to the lowering of the energy of singlet dianion state due to hydrogen bonding effects. The effect of the amino group on the doublet monoanion state is more complicated, and results in the weakening of the binding of the adjacent carboxylate group due to electronic structure resonance effects. This conclusion is confirmed by the analysis of NIPES results that show enhanced production of near zero kinetic energy electrons observed experimentally for amine-functionalized species.
Popescu, M R; Trană, F; Manolea, H; Rauten, Ane-Marie; Șurlin, Petra; Dragomir, L P
2014-01-01
The partially intercalated edentation offers the practitioner the possibility of the functional rehabilitation of the dental arcades through conjunct gnato-prosthetic devices. The functions of the dento-maxilar device, disturbed by the presence of edentation, require a treatment approach so that, without pre-planning or estimating, the result can lead most of the times to failure in terms of functionality. Clinical evaluation associated with pre- and proprosthetic treatment can also impose, in some situations the evaluation of the dental units involved in prosthetic rehabilitation. The association and implementation of the prosthetic construction in the occlusive-articular ensemble, as well as the counterbalancing of the mastication forces per dental unit and whole interarch system, linked to the distribution of the forces at the level of the pillar teeth and prosthetic construction, represent the goal of this theoretical study.
Synthesis and density functional theoretical study of steroidal spiro-triazolidinone.
Sharma, Kamlesh; Lal, Bhajan
2008-06-01
The reaction of 3beta-chloro-5alpha-cholestan-6-one semicarbazone 1 with hydrogen peroxide at 0 degrees C gives 3beta-chloro-5alpha-cholestan-6-spiro-1',2',4'-triazolidine-3'-one 2 as a product. The structural assignment of the product was confirmed on the basis of its elemental, analytical and spectral data. The ab initio calculations were performed by using density functional theory (DFT) at B3LYP/6-31G* basis set in order to describe a free radical reaction mechanism. The reaction proceeds through two radical intermediates formation. The mechanism of the reaction was explained by using frontier molecular orbital (FMO), spin electronic density map, encoded electrostatic potential map and atomic charges. It was found that the localization of frontier orbitals and the flow of atomic charges of all the calculated structures support the present reaction mechanism. The molecular properties like total energy, dipole moment and hardness of each optimized structure, were also explained. Stability of all the optimized structures in this study was supported by their respective fundamental frequencies and energy minima.
Theoretical study of Structural and analytical potential energy functions of GaN
Institute of Scientific and Technical Information of China (English)
无
2007-01-01
Using Density Function Theory,the present work has optimized the equilibrium geometry of GaN. Murrell-Sorbie analytical potential energy functions of GaN have been derived by using ab initio data and the least-square fitting method,and harmonic frequency,force constant and spectroscopic data also have been calculated.
Institute of Scientific and Technical Information of China (English)
WANG; Zhengwu; GUO; Baomin; ZHANG; Gexin
2006-01-01
The iterative method in functional analysis is applied to looking for a solution of the Poisson-Boltzmann equation in order to describe the problems of the distribution of the potentials in the electric double layer (EDL) inside the water pool for a cylindrical inverse micelle. Potentials as a function of the position of a particular point in EDL are computed, which display a quantitative is also shown that in the higher-potential range the iterative calculations can give more accurate results. These results indicate the utility of this functional analysis technique in the description of the properties of EDL for a cylindrical inverse micelle.
Study of the Electrical Double Layer of a Spherical Micelle:Functional Theoretical Approach
Institute of Scientific and Technical Information of China (English)
无
2001-01-01
By using the iterative method in functional theory, an analytic expression of the Poisson-Boltzmann equation (PB eq.), which describes the distribution of the potential of electrical double layer of a spherical micelle, has been carried out under the general potential condition for the first time. The method also can give the radius, the surface potential, and the thickness of the layer.
Study on Electric Double Layer of a Cylindrical Particle with Functional Theoretical Approach
Institute of Scientific and Technical Information of China (English)
WANG,Zheng-Wu; LIU,Xue-Min; YU,Hui-Xin; ZHOU,Ming; JIN,Jian
2007-01-01
A new method, i.e. the iterative method in functional theory, was introduced to solve analytically the nonlinear Poisson-Boltzmann (PB) equation under general potential ψ condition for the electric double layer of a charged cylindrical colloid particle in a symmetrical electrolyte solution. The iterative solutions of ψ are expressed as functions of the distance from the axis of the particle with solution parameters: the concentration of ions c, the aggregation number of ions in a unit length m, the dielectric constant ε, the system temperature T and so on. The relative errors show that generally only the first and the second iterative solutions can give accuracy higher than 97%. From the second iterative solution the radius and the surface potential of a cylinder have been defined and the corresponding values have been estimated with the solution parameters. Furthermore, the charge density, the activity coefficient of ions and the osmotic coefficient of solvent were also discussed.
Theoretical structure and vibrational spectra of ciprofloxacin: Density functional theory study
Yang, Yue; Gao, Hongwei
2013-02-01
The molecular structure and vibrational spectra of ciprofloxacin(1-cyclopropyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-piperazinyl)-3-quinolinecarboxylic acid) have been calculated using the different density functional theory (DFT) methods and various basis sets. This paper examines the comparative performance of different DFT methods at various basis sets in predicting molecular and vibrational spectra of ciprofloxacin. The calculation results show that SVWN/LANL2DZ level and SVWN/6-31G level offer the highest certainty to predict the structure and vibrational spectra of ciprofloxacin, respectively.
Theoretical study of the structural stability for fcc-CHx phases using density functional theory
Directory of Open Access Journals (Sweden)
M Dadsetani
2011-09-01
Full Text Available Recently, a new carbon modification, namly n-diamond, have been reported, whose structure is still a matter of debate. It is important to note that the synthesis of n-diamond was carried out in the presence of hydrogen or methan. In this work we evaluate the structural stability of five fcc-CHx phases by means of first-principle calculation. The total energy is obtained as a function of the isotropic, tetragonal and rhombohedral deformations for the bulk structures. First, we analyze the C2H (cuprite, CH (zincblende, CH (rocksalt and CH2 (fluorite structures.It is found that the four systems show a minimum in the total energy for the isotropic and rhombohedral deformations, but are unstable against tetragonal deformation. In the second part, we explore the structural stability of CH2 in the pyrite structure. We find that CH2 (pyrite with the hydrogen atoms defined by the internal parameter u=0.35 and a lattice parameter of 3.766 Å is elastically stable, providing a possible explanation for the experimental observation of fcc-carbon in materials prepared in the presence of hydrogen or methan. In final, we calculate density of states, band structure and EELS spectrum of CH2 (pyrite and compare them with n-diamond.
Theoretical study on the reaction of CN radicals with ClO radicals by density functional theory
Institute of Scientific and Technical Information of China (English)
YANG YuHong; HUANG XuRi; SUN ChiaChung
2009-01-01
The reaction mechanism of CN radicals with CIO radicals has been studied theoretically using ab initio and density functional theory (DFT).The result shows that the main reaction path is the O atom in radical CIO attacks the C atom in radical CN to compose the intermediate 1 CIOCN.Three thermodynamically accessible prodncts,P_1 (CO+CIN),P_3 (NO+CCI),and P_4 (CINCO),were obtained from intermediate 1 through isomerization and decomposition reactions.P_4 is the primary product,and P_1 and P_3 are the secondary product.Compared with the singlet potential energy surface,the contribution of the triplet potential energy surface can be ignored.
Theoretical study on the reaction of CN radicals with ClO radicals by density functional theory
Institute of Scientific and Technical Information of China (English)
无
2009-01-01
The reaction mechanism of CN radicals with ClO radicals has been studied theoretically using ab initio and density functional theory(DFT).The result shows that the main reaction path is the O atom in radical ClO attacks the C atom in radical CN to compose the intermediate 1 ClOCN.Three thermodynamically accessible prodncts,P1(CO+ClN),P3(NO+CCl),and P4(ClNCO),were obtained from intermediate 1 through isomerization and decomposition reactions.P4 is the primary product,and P1 and P3 are the secondary product.Compared with the singlet potential energy surface,the contribution of the triplet potential energy surface can be ignored.
Theoretical study of the dipole moment function of the X2Sigma(+) state of CN. [in comets
Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.
1989-01-01
The X2Sigma(+) state dipole moment function of CN is determined from accurate ab initio calculations. The calculated Einstein coefficient of 13.0 /s for the fundamental 1-0 vibrational band is in excellent agreement with the value measured by Treffers (1975) using a King furnace. The theoretical vibrational band strengths should be valuable in interpreting the fluorescence spectrum of CN in comets.
Gupta, Mayuri; da Silva, Eirik F; Hartono, Ardi; Svendsen, Hallvard F
2013-08-15
Temperature dependent correlations for enthalpy of deprotonation, carbamate formation, and heat of absorption of the overall reaction between aqueous MEA and MDEA and gaseous CO2 are calculated on the basis of computational chemistry based ln K values input to the Gibbs-Helmholtz equation. Temperature dependency of reaction equilibrium constants for deprotonation and carbamate formation reactions is calculated with the SM8T continuum solvation model coupled with density functional theoretical calculations at the B3LYP/6-311++G(d,p) level of theory. Calculated reaction equilibrium constants and enthalpies of individual reactions and overall heat of absorption are compared against experimental data in the temperature range 273.15-373 K. Temperature dependent correlations for different reaction equilibrium constants and enthalpies of reactions are given. These correlated results can be used in thermodynamic models such as UNIQUAC and NRTL for better understanding of post-combustion CO2 capture solvent chemistry.
Wu, Wenjie; Wu, Zemin; Rong, Chunying; Lu, Tian; Huang, Ying; Liu, Shubin
2015-07-23
The electrophilic aromatic substitution for nitration, halogenation, sulfonation, and acylation is a vastly important category of chemical transformation. Its reactivity and regioselectivity is predominantly determined by nucleophilicity of carbon atoms on the aromatic ring, which in return is immensely influenced by the group that is attached to the aromatic ring a priori. In this work, taking advantage of recent developments in quantifying nucleophilicity (electrophilicity) with descriptors from the information-theoretic approach in density functional reactivity theory, we examine the reactivity properties of this reaction system from three perspectives. These include scaling patterns of information-theoretic quantities such as Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy and information gain at both molecular and atomic levels, quantitative predictions of the barrier height with both Hirshfeld charge and information gain, and energetic decomposition analyses of the barrier height for the reactions. To that end, we focused in this work on the identity reaction of the monosubstituted-benzene molecule reacting with hydrogen fluoride using boron trifluoride as the catalyst in the gas phase. We also considered 19 substituting groups, 9 of which are ortho/para directing and the other 9 meta directing, besides the case of R = -H. Similar scaling patterns for these information-theoretic quantities found for stable species elsewhere were disclosed for these reactions systems. We also unveiled novel scaling patterns for information gain at the atomic level. The barrier height of the reactions can reliably be predicted by using both the Hirshfeld charge and information gain at the regioselective carbon atom. The energy decomposition analysis ensued yields an unambiguous picture about the origin of the barrier height, where we showed that it is the electrostatic interaction that plays the dominant role, while the roles played by exchange-correlation and
Indian Academy of Sciences (India)
Heidar Raissi; Mehdi Yoosefian; Effat Moshfeghi; Farzaneh Farzad
2012-05-01
The characteristics of the intramolecular hydrogen bonding for a series of 19 different derivatives of -aminoacroleine have been systematically analysed at the B3LYP/6-31G∗∗ level of theory. The topological properties of the electron density distributions for N-H$\\cdots$O intramolecular bridges have been analysed by the Bader theory of atoms in molecules. The electron density () and Laplacian (∇2 ρ) properties at critical points of the relevant bonds, estimated by AIM calculations, showed that N-H$\\cdots$O have low and positive character (∇2 ρ > 0), consistent with electrostatic character of the hydrogen bond. The vibrational study of the hydrogen bonded systems showed negative (red) shifts for the (N−H) stretching mode. The -electron delocalization parameter () as a geometrical indicator of a local aromaticity and the geometry-based HOMA have also been calculated. Furthermore, the analysis of hydrogen bond in this molecule and its derivatives by natural bond orbital (NBO) methods support the DFT results. The results of AIM and NBO analysis as well as (N−H) were further used for estimation of the hydrogen bonding interactions and the forces driving their formation. The various correlations were found between geometrical, energetic and topological parameters. The substituent effect was also analysed and it was found that the strongest hydrogen bonds exist for N+(CH3)3 and Cl substituents while the weakest ones for COOCH3.
Theoretical Advanced Study Institute: 2014
Energy Technology Data Exchange (ETDEWEB)
DeGrand, Thomas [Univ. of Colorado, Boulder, CO (United States)
2016-08-17
The Theoretical Advanced Study Institute was held at the University of Colorado, Boulder, during June 2-27, 2014. The topic was "Journeys through the Precision Frontier: Amplitudes for Colliders." The organizers were Professors Lance Dixon (SLAC) and Frank Petriello (Northwestern and Argonne). There were fifty one students. Nineteen lecturers gave sixty seventy five minute lectures. A Proceedings was published.
2001-01-01
The adsorption of H And S2- species on Pd (100) has been studied with ab initio, density-functional calculations and electrochemical methods. A cluster of five Pd atoms with a frozen geometry described the surface. The computational calculations were performed through the GAUSSIAN94 program, and the basis functions adapted to a pseudo-potential obtained by using the Generator Coordinate Method adapted to the this program. Using the cyclic voltammetry technique through a Model 283 Potentiostat...
Wang, Zengwei; Zhu, Ping
2017-07-01
In this paper, a general method using in-situ frequency response functions (FRFs) is proposed for predicting operational responses of modified mechanical systems. In the method responses of modified mechanical systems can be calculated by using the delta dynamic stiffness matrix, the subsystem FRF matrix and responses of the original system, even though operational forces are unknown. The proposed method is derived theoretically in a general form as well as for six specific scenarios. The six scenarios correspond respectively to: (a) modifications made on the mass; (b) changes made on the stiffness values of the link between a degree-of-freedom (DOF) and the ground; (c) the fully rigid link between a DOF and the ground; (d) changes made on the stiffness values of the link between two DOFs; (e) the null link between two DOFs and (f) the fully rigid link between two DOFs. It is found that for scenarios (a), (b) and (d) the delta dynamic stiffness matrix is required when predicting responses of the modified mechanical system. But for scenarios (c), (e) and (f), no delta dynamic stiffness matrix is required and the new system responses can be calculated solely using the subsystem FRF matrix and responses of the original system. The proposed method is illustrated by a numerical example and validated using data generated by finite element simulations. The work in this paper will be beneficial to solving vibration and noise engineering problems.
Theoretical Studies of Reaction Surfaces
2007-11-02
Similar levels of agreement are being found in studies of water clusters12 , the Menshutkin reaction 13 (ion separation reaction ), a prototypical SN2 ...of both reactants and products. These analyses reveal that Bery pseudorotation occurs repeatedly during the side attack, whereas the SN2 reaction H...31 Aug 97 4. TITLE AND SUBTITLE 5. FUNDING NUMBERS AASERT93 THEORETICAL STUDIES OF REACTION SURFACES F49620-93-1-0556 3484/XS 6. AUTHOR(S) 61103D DR
Theoretical Studies of Silicon Chemistry
1990-02-01
Molecular and Electronic Structure of Silyl Nitrene , M.S. Gordon, Chem. Phys. Lett., 146, 148 (1988). 18. A Theoretical Study of the Three-Membered Rings...phase and crystal structures. Of course, all three possibilities may contribute. B. The Electronic and Molecular Structure of Silyl Nitrene , M.S...a silaimine. An interesting question regarding the primary process is whether the silyl nitrene , R3SiN, is formed as an intermediate. As a first step
Theoretical determination of cesiated work functions
Szejn, R. M.
1972-01-01
A computer program based on the theoretical work of Gyftopoulos, Steiner, and Levine on bimetallic systems and using a modified version of Wilkins' SIMCON subroutine SURFAS was written for the Univac 1108. This program, WFGSL, accepts the operating conditions and the physical parameters pertinent to the substrate and adsorbate, and outputs the field-free work function, electron current (Richardson equation), ion current (Saha equation), and fractional substrate coverage by the adsorbate. A brief description of the theory is presented together with a program description and listing. An application of the program to a bimetallic system of cesium (adsorbate) and rhenium (substrate) is also described.
CO oxidation on gold nanoparticles: Theoretical studies
DEFF Research Database (Denmark)
Remediakis, Ioannis; Lopez, Nuria; Nørskov, Jens Kehlet
2005-01-01
We present a summary of our theoretical results regarding CO oxidation on both oxide-supported and isolated gold nanoparticles. Using Density Functional Theory we have studied the adsorption of molecules and the oxidation reaction of CO on gold clusters. Low-coordinated sites on the gold...
Wang, Hong-mei; Liu, Yue-jie; Wang, Hong-xia; Zhao, Jing-xiang; Cai, Qing-hai; Wang, Xuan-zhang
2013-12-01
Motivated by the great advance in graphene hydroxide--a versatile material with various applications--we performed density functional theory (DFT) calculations to study the functionalization of the two-dimensional hexagonal boron nitride (h-BN) sheet with hydroxyl (OH) radicals, which has been achieved experimentally recently. Particular attention was paid to searching for the most favorable site(s) for the adsorbed OH radicals on a h-BN sheet and addressing the roles of OH radical coverage on the stability and properties of functionalized h-BN sheet. The results indicate that, for an individual OH radica, the most stable configuration is that it is adsorbed on the B site of the h-BN surface with an adsorption energy of -0.88 eV and a magnetic moment of 1.00 μ(B). Upon adsorption of more than one OH radical on a h-BN sheet, however, these adsorbates prefer to adsorb in pairs on the B and its nearest N atoms from both sides of h-BN sheet without magnetic moment. An energy diagram of the average adsorption energy of OH radicals on h-BN sheet as a function of its coverage indicates that when the OH radical coverage reaches to 60 %, the functionalized h-BN sheet is the most stable among all studied configurations. More importantly, this configuration exhibits good thermal and dynamical stability at room temperature. Owing to the introduction of certain impurity levels, the band gap of h-BN sheet gradually decreases with increasing OH coverage, thereby enhancing its electrical conductivity.
Theoretical Advanced Study Institute: 2014
Energy Technology Data Exchange (ETDEWEB)
DeGrand, Thomas [Univ. of Colorado, Boulder, CO (United States)
2016-08-17
The Theoretical Advanced Study Institute (TASI) was held at the University of Colorado, Boulder, during June 2-27, 2014. The topic was "Journeys through the Precision Frontier: Amplitudes for Colliders." The organizers were Professors Lance Dixon (SLAC) and Frank Petriello (Northwestern and Argonne). There were fifty-one students. Nineteen lecturers gave sixty seventy-five minute lectures. A Proceedings was published. This TASI was unique for its large emphasis on methods for calculating amplitudes. This was embedded in a program describing recent theoretical and phenomenological developments in particle physics. Topics included introductions to the Standard Model, to QCD (both in a collider context and on the lattice), effective field theories, Higgs physics, neutrino interactions, an introduction to experimental techniques, and cosmology.
Theoretical studies of combustion dynamics
Energy Technology Data Exchange (ETDEWEB)
Bowman, J.M. [Emory Univ., Atlanta, GA (United States)
1993-12-01
The basic objectives of this research program are to develop and apply theoretical techniques to fundamental dynamical processes of importance in gas-phase combustion. There are two major areas currently supported by this grant. One is reactive scattering of diatom-diatom systems, and the other is the dynamics of complex formation and decay based on L{sup 2} methods. In all of these studies, the authors focus on systems that are of interest experimentally, and for which potential energy surfaces based, at least in part, on ab initio calculations are available.
Directory of Open Access Journals (Sweden)
*B. Semire
2012-12-01
Full Text Available Theoretical calculations using Density Functional Theory (DFT were performed on 2,5-bis[4-N,N-diethylaminostyryl]thiophene and its furan and pyrrole derivatives The energy band gaps calculated at B3LYP/6-31G(d level for thiophene derivatives are lower than that of furan and pyrrole analogues. The absorption λmax calculated using DFT was shifted to longer wavelength by replacement of R = CH3 by C2H5 for all studied molecules. The geometries and electronic properties of the compounds were also studied.
Institute of Scientific and Technical Information of China (English)
LI Xiao-Hong; TANG Zheng-Xin; Abraham F.Jalbout; ZHANG Xian-Zhou; CHENG Xin-Lu
2008-01-01
The N-NO2 bond dissociation energies (BDEs) for 7 energetic materials were computed by means of accurate density functional theory (B3LYP, B3PW91 and B3P86) with 6-31G** and 6-311G** basis sets. By comparing the computed energies and experimental results, we find that the B3P86/6-311G** method can give good results of BDE, which has the mean absolute deviation of 1.30 kcal/mol. In addition, substituent effects were also taken into account. It is noted that the Hammett constants of substituent groups are related to the BDEs of the N-NO2 bond and the bond dissociation energies of the energetic materials studied decrease when increasing the number of NO2 group.
THEORETICAL ASPECTS OF FILMMUSIC STUDY
Directory of Open Access Journals (Sweden)
Egorova Tatiana K.
2014-04-01
Full Text Available In this article, author analyzes the theoretical aspects of the film music study taking into account with modern realities in the development of world film-process and attempts to its scientific understanding. Need for innovation in this area is long overdue, because the existing on this topic nonfiction no longer meets the new aesthetic and art-practical achievements and innovations in the film music development at the XXI century. Related to the phenomenon of music in screen arts a number of new terms and concepts require a certain adjustment as well. Their range of action is not yet fully defined. Author of the article offered her version of their content-semantic interpretation (largely experimental designed to promote new research methods for the film music study.
Moradi, M; Divsalar, A; Saboury, A A; Ghalandari, B; Harifi, A R
2015-01-01
Deferasirox (DFX), as an oral chelator, is used for treatment of transfusional iron overload. In this study, we have investigated the effects of DFX as an iron chelator, on the function and structure of bovine liver catalase (BLC) by different spectroscopic methods of UV-visible, fluorescence, and circular dichroism (CD) at two temperatures of 25 and 37 °C. In vitro kinetic studies showed that DFX can inhibit the enzymatic activity in a competitive manner. KI value was calculated 39 nM according to the Lineweaver-Burk plot indicating a high rate of inhibition of the enzyme. Intrinsic fluorescence data showed that increasing the drug concentrations leads to a significant decrease in the intrinsic emission of the enzyme indicating a significant change in the three-dimensional environment around the chromophores of the enzyme structure. By analyzing the fluorescence quenching data, it was found that the BLC has two binding sites for DFX and the values of binding constant at 25 and 37 °C were calculated 1.7 × 10(7) and 3 × 10(7) M(-1), respectively. The static type of quenching mechanism is involved in the quenching of intrinsic emission of enzyme. The thermodynamic data suggest that hydrophobic interactions play a major role in the binding reaction. UV-vis spectroscopy results represented the changes in tryptophan (Trp) absorption and Soret band spectra, which indicated changes in Trp and heme group position caused by the drug binding. Also, CD data represented that high concentrations of DFX lead to a significant decreasing in the content of β-sheet and random coil accompanied an increasing in α-helical content of the protein. The molecular docking results indicate that docking may be an appropriate method for prediction and confirmation of experimental results and also useful for determining the binding mechanism of proteins and drugs. According to above results, it can be concluded that the DFX can chelate the Fe(III) on the enzyme active site leading
Arul Dhas, D.; Hubert Joe, I.; Roy, S. D. D.; Balachandran, S.
2015-01-01
A widespread exploration on the intra-molecular charge transfer interaction through an efficient π-conjugated path from a strong electron-donor group (amino) to a strong electron-acceptor group (nitro) has been carried out using FTIR, FT-Raman, UV-Vis, fluorescence and NMR spectra on insecticide compound 4-benzyloxy-2-nitroaniline. Density functional theory method is used to determine optimized molecular geometry, harmonic vibrational wavenumbers and intensities using 6-311G(d,p) basis set by means of Gaussian 09W program suit. A comprehensive investigation on the sp2 to sp3 hybridization and non-planarity property has been performed. Natural bond orbital analysis is used to study the existence of C-H⋯O, N-H⋯O and C-H⋯π proper and improper hydrogen bonds. The HOMO and LUMO analysis reveals the possibility of charge transfer within the molecule. A complete assignment of the experimental absorption peaks in the ultraviolet region has also been performed. Isotropic chemical shifts of 13C, 1H, 15N and 18O NMR and nuclear spin-spin coupling constants have been computed using the gauge-invariant atomic orbital method. The biological activity of substituent amino and nitro groups are evident from the hydrogen bonds through which the target amino acids are linked to the drug as evidenced from molecular docking.
Sun, Yubing; Yang, Shubin; Chen, Yue; Ding, Congcong; Cheng, Wencai; Wang, Xiangke
2015-04-01
The adsorption and desorption of U(VI) on graphene oxides (GOs), carboxylated GOs (HOOC-GOs), and reduced GOs (rGOs) were investigated by batch experiments, EXAFS technique, and computational theoretical calculations. Isothermal adsorptions showed that the adsorption capacities of U(VI) were GOs > HOOC-GOs > rGOs, whereas the desorbed amounts of U(VI) were rGOs > GOs > HOOC-GOs by desorption kinetics. According to EXAFS analysis, inner-sphere surface complexation dominated the adsorption of U(VI) on GOs and HOOC-GOs at pH 4.0, whereas outer-sphere surface complexation of U(VI) on rGO was observed at pH 4.0, which was consistent with surface complexation modeling. Based on the theoretical calculations, the binding energy of [G(···)UO2](2+) (8.1 kcal/mol) was significantly lower than those of [HOOC-GOs(···)UO2](2+) (12.1 kcal/mol) and [GOs-O(···)UO2](2+) (10.2 kcal/mol), suggesting the physisorption of UO2(2+) on rGOs. Such high binding energy of [GOs-COO(···)UO2](+) (50.5 kcal/mol) revealed that the desorption of U(VI) from the -COOH groups was much more difficult. This paper highlights the effect of the hydroxyl, epoxy, and carboxyl groups on the adsorption and desorption of U(VI), which plays an important role in designing GOs for the preconcentration and removal of radionuclides in environmental pollution cleanup applications.
Institute of Scientific and Technical Information of China (English)
Ren Tingzhi; Liu Cai
2004-01-01
A new non-sinusoidal oscillation waveform is constructed for controlling the mold oscillation during continuous casting. Casting velocity and oscillation parameters are then established for a computer model of the continuous casting process. The waveform distortion coefficient ε of waveform function is close to the waveform distortion rate α, so ε is taken for ε when the basic parameters are selected initially. The waveform function can be created for the servo hydraulic system or the mechanical driving system. Industrial scale experiments show the waveform function is effective.
Theoretical Studies of Proton Radioactivity
Institute of Scientific and Technical Information of China (English)
Ldia S Ferreira; Enrico Maglione
2016-01-01
In the paper, we will discuss the most recent theoretical approaches developed by our group, to understand the mechanisms of decay by one proton emission, and the structure and shape of exotic nuclei at the limits of stability.
Sajan, D.; Udaya Lakshmi, K.; Erdogdu, Y.; Hubert Joe, I.
2011-01-01
The near-infrared Fourier transform (NIR-FT) Raman and Fourier transform infrared (FT-IR) spectral analyses of 2,6-bis(benzylidene)cyclohexanone (BBC) molecule, a potential drugs for the treatment of P388 leukemia cells, were carried out along with density functional computations. The optimized geometry of BBC using density functional theory shows that the energetically favored chair conformation is not observed for central cyclohexanone ring and is found to possess a nearly 'half chair' conformation and shows less expansion of the angles and more rotation about the bonds. The existence of intramolecular C-H⋯O improper, blue-shifted hydrogen bond was investigated by means of the NBO analysis. The lowering of carbonyl stretching vibration can be attributed to the mesomeric effect and the π-orbital conjugation induced by the unsaturation in the α-carbon atoms and co-planarity of the (-CH dbnd C-(C dbnd O)-C dbnd CH-) group.
Liu, Xiaoting; Zhang, Jilong; Li, Kai; Sun, Xiaobo; Wu, Zhijian; Ren, Aimin; Feng, Jikang
2013-04-01
Special attention has been paid to understanding the structural effect on electronic structure and absorption spectra for an extensive series of functionalized aza-BODIPY molecules. We have employed the quadratic response theory as well as a sum-over-states approach involving few intermediate states to calculate the two-photon cross section (δmax). The results suggest that chemical modifications on the aza-BODIPY core and peripheral moieties using various substituents can finely tune their linear and nonlinear optical properties. Therefore, some new fluorophores absorbing in the near infrared region and featuring considerably high δmax at telecommunication wavelengths are proposed, which are excellent candidates for nonlinear transmission and fluorescent labeling materials. The investigation contributes a useful starting point for further design of more effective aza-BODIPY dyes and can be valuable as a foundation for future experimental research and development.
Villamena, Frederick A; Hadad, Christopher M; Zweier, Jay L
2004-02-18
The hydroxyl radical (*OH) is an important mediator of biological oxidative stress, and this has stimulated interest in its detection. 5,5-Dimethyl-1-pyrroline N-oxide (DMPO) and its alkoxycarbonyl and alkoxyphosphoryl analogues have been employed as spin traps for electron paramagnetic resonance (EPR) spectroscopic radical detection. Energies of optimized geometries of nitrones and their corresponding *OH adducts were calculated using density functional theory (DFT) at the B3LYP/6-31+G//B3LYP/6-31G level. Calculations predict that the trans adduct formation is favored in alkoxycarbonyl nitrones, while cis adducts with intramolecular H-bonding is favored for alkoxyphosphoryl nitrones. Addition of *OH to a phosphoryl-substituted nitrone is more exoergic than the carbonylated nitrones. Charge and spin densities on the nitrone spin traps were correlated with their rates of addition with *OH, and results show that the charge density on the nitronyl C, the site of *OH addition, is more positive in phosphorylated nitrones compared to DMPO and the alkoxycarbonyl nitrones. The dihedral angle between the beta-H and nitroxyl O bonds is smaller in phosphorylated nitrones, and that aspect appears to account for the longer half-lives of the spin adducts compared to those in DMPO and alkoxycarbonyl nitrones. Structures of nitrones with trifluoromethyl-, trifluoromethylcarbonyl-, methylsulfonyl-, trifluoromethylsulfonyl-, amido-, spiropentyl-, and spiroester substituents were optimized and their energies compared. Amido and spiroester nitrones were predicted to be the most suitable nitrones for spin trapping of *OH due to the similarity of their thermodynamic and electronic properties to those of alkoxyphosphoryl nitrones. Moreover, dimethoxyphosphoryl substitution at C-5 was found to be the most efficient substitution site for spin trapping of *OH, and their spin adducts are predicted to be the most stable of all of the isomeric forms.
Directory of Open Access Journals (Sweden)
F.Z. MIMOUNI
2013-03-01
Full Text Available The isolation of the pair atropisomers of the both iminothiazoline derivatives and the spectroscopic analytical of the compound have been computed using B3LYP/6-31G(d,p level to derive the equilibrium geometry, conformational stability, molecular orbital energies and vibrational frequencies was studied in this paper.
Theoretical Studies of Nanocluster Formation
2016-05-26
5f. WORK UNIT NUMBER Q188 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION REPORT NO. Air Force Research...For presentation at AFOSR Molecular Dynamics and Theoretical Chemistry Program Review; Arlington, VA (25 May 2016) PA Case Number: #16215; Clearance...Approved for public release; Distribution Unlimited. PA Clearance No: 16215 This briefing contains information up to: 2 Outline 1. Introduction
CO oxidation on gold nanoparticles: Theoretical studies
DEFF Research Database (Denmark)
Remediakis, Ioannis; Lopez, Nuria; Nørskov, Jens Kehlet
2005-01-01
We present a summary of our theoretical results regarding CO oxidation on both oxide-supported and isolated gold nanoparticles. Using Density Functional Theory we have studied the adsorption of molecules and the oxidation reaction of CO on gold clusters. Low-coordinated sites on the gold...... nanoparticles can adsorb small inorganic molecules such as O2 and CO, and the presence of these sites is the key factor for the catalytic properties of supported gold nanoclusters. Other contributions, induced by the presence of the support, can provide parallel channels for the reaction and modulate the final...
Theoretical study on a water muffler
Du, T.; Chen, Y. W.; Miao, T. C.; Wu, D. Z.
2016-05-01
Theoretical computation on a previously studied water muffler is carried out in this article. Structure of the water muffler is composed of two main parts, namely, the Kevlar- reinforced rubber tube and the inner-noise-reduction structure. Rubber wall of the rubber tube is assumed to function as rigid wall lined with sound absorption material and is described by a complex radial wave number. Comparison among the results obtained from theoretical computation, FEM (finite element method) simulation and experiment of the rubber tube and that of the water muffler has been made. The theoretical results show a good accordance in general tendency with the FEM simulated and the measured results. After that, parametric study on the diameter of the inner structure and that of the rubber tube is conducted. Results show that the diameter of the left inner structure has the most significant effect on the SPL of the water muffler due to its location and its effect on the diameter ratio D2/D1.
Theoretical Study of Dinoflagellate Bioluminescence.
Wang, Ming-Yu; Liu, Ya-Jun
2017-03-01
Dinoflagellates are the most ubiquitous luminescent protists in the marine environment and have drawn much attention for their crucial roles in marine ecosystems. Dinoflagellate bioluminescence has been applied in underwater target detection. The luminescent system of dinoflagellates is a typical luciferin-luciferase one. However, the excited-state oxyluciferin is not the light emitter of dinoflagellate bioluminescence as in most luciferin-luciferase bioluminescent organisms. The oxyluciferin of bioluminescent dinoflagellates is not fluorescent, whereas its luciferin emits bright fluorescence with similar wavelength of the bioluminescence. What is the light emitter of dinoflagellate bioluminescence and what is the chemical process of the light emission like? These questions have not been answered by the limited experimental evidence so far. In this study, for the first time, the density functional calculation is employed to investigate the geometries and properties of luciferin and oxyluciferin of bioluminescent dinoflagellate. The calculated results agree with the experimental observations and indicate the luciferin or its analogue, rather than oxyluciferin, is the bioluminophore of dinoflagellate bioluminescence. A rough mechanism involving energy transfer is proposed for dinoflagellate bioluminescence.
Tuoc, Vu Ngoc; Doan Huan, Tran; Viet Minh, Nguyen; Thi Thao, Nguyen
2016-06-01
Polymorphs or phases - different inorganic solids structures of the same composition usually have widely differing properties and applications, thereby synthesizing or predicting new classes of polymorphs for a certain compound is of great significance and has been gaining considerable interest. Herein, we perform a density functional theory based tight binding (DFTB) study on theoretical prediction of several new phases series of II-VI semiconductor material ZnO nanoporous phases from their bottom-up building blocks. Among these, three phases are reported for the first time, which could greatly expand the family of II- VI compound nanoporous phases. We also show that all these generally can be categorized similarly to the aluminosilicate zeolites inorganic open-framework materials. The hollow cage structure of the corresponding building block ZnkOk (k= 9, 12, 16) is well preserved in all of them, which leads to their low-density nanoporous and high flexibility. Additionally the electronic wide-energy gap of the individual ZnkOk is also retained. Our study reveals that they are all semiconductor materials with a large band gap. Further, this study is likely to be the common for II-VI semiconductor compounds and will be helpful for extending their range of properties and applications.
Studies in theoretical particle physics
Energy Technology Data Exchange (ETDEWEB)
Kaplan, D.B.
1991-07-01
This proposal focuses on research on three distinct areas of particle physics: (1) Nonperturbative QCD. I tend to continue work on analytic modelling of nonperturbative effects in the strong interactions. I have been investigating the theoretical connection between the nonrelativistic quark model and QCD. The primary motivation has been to understand the experimental observation of nonzero matrix elements involving current strange quarks in ordinary matter -- which in the quark model has no strange quark component. This has led to my present work on understanding constituent (quark model) quarks as collective excitations of QCD degrees of freedom. (2) Weak Scale Baryogenesis. A continuation of work on baryogenesis in the early universe from weak interactions. In particular, an investigation of baryogenesis occurring during the weak phase transition through anomalous baryon violating processes in the standard model of weak interactions. (3) Flavor and Compositeness. Further investigation of a new mechanism that I recently discovered for dynamical mass generation for fermions, which naturally leads to a family hierarchy structure. A discussion of recent past work is found in the next section, followed by an outline of the proposed research. A recent publication from each of these three areas is attached to this proposal.
Theoretical Studies of Metal Oxides.
1981-10-01
obtained from the tables of atomic wavefunctions of Clementi and Roetti. The *~ 21Mg basis used was the ground state Mg(3s , S) set supplemented with...MgO+ has been started. The basis set was obtained + 2 4 3 from Clementi and Roetti’s tables for Mg (3s, S) and O(2p , p). Polarization functions were
Theoretical numerical analysis a functional analysis framework
Atkinson, Kendall
2005-01-01
This textbook prepares graduate students for research in numerical analysis/computational mathematics by giving to them a mathematical framework embedded in functional analysis and focused on numerical analysis. This helps the student to move rapidly into a research program. The text covers basic results of functional analysis, approximation theory, Fourier analysis and wavelets, iteration methods for nonlinear equations, finite difference methods, Sobolev spaces and weak formulations of boundary value problems, finite element methods, elliptic variational inequalities and their numerical solu
Institute of Scientific and Technical Information of China (English)
Zheng Guo Huang; Li Zhou; En Cui Yang
2008-01-01
Density functional theoretical calculations have been made on the electronic structure of (CH)n(BCO)6-n(n=0-6) at B3LYP/6-311 + G(d) level.The nuclear-independent chemical shifts (NICS) values calculated using the gauge-including atomic orbitals (GIAO) method were used to assess on the aromaticities of these molecules.The results shows that (CH)n(BCO)6-n(n=0-6)species are aromatic.
Special functions group theoretical aspects and applications
Schempp, Walter; Askey, Richard A
1984-01-01
Approach your problems from It isn't that they can't see the right end and begin with the solution. the answers. Then one day, It is that they can't see the perhaps you will find the problem. final question. G.K. Chesterton. The Scandal 'The Hermit Clad in Crane of Father Brown 'The Point of Feathers' in R. van Gulik's a Pin'. The Chinese Maze Murders. Growing specialization and diversification have brought a host of monographs and textbooks on increasingly specialized topics. However, the "tree" of knowledge of mathematics and related fields does not grow only by putting forth new branches. It also happens, quite often in fact, that branches which were thought to be completely disparate are suddenly seen to be related. Further, the kind and level of sophistication of mathematics applied in various sciences has changed drastically in recent years: measure theory is used (non-trivially) in regional and theoretical economics; algebraic geometry interacts with physics; the Minkowsky lemma, coding theory and the ...
Medial Cochlear Efferent Function: A Theoretical Analysis
Mountain, David C.
2011-11-01
Since the discovery of the cochlear efferent system, many hypotheses have been put forth for its function. These hypotheses for its function range from protecting the cochlea from over stimulation to improving the detection of sounds in noise. It is known that the medial efferent system innervates the outer hair cells and that stimulation of this system reduces basilar membrane and auditory nerve sensitivity which suggests that this system acts to decrease the gain of the cochlear amplifier. Here I present modeling results as well as analysis of published experimental data that suggest that the function of the medial efferent reflex is to decrease the cochlear amplifier gain by just the right amount so that the nonlinearity in the basilar membrane response lines up perfectly with the inner hair cell nonlinear transduction process to produce a hair cell receptor potential that is proportional to the logarithm of the sound pressure level.
Theoretical studies of unconventional superconductors
Energy Technology Data Exchange (ETDEWEB)
Groensleth, Martin Sigurd
2008-07-01
This thesis presents four research papers. In the first three papers we have derived analytical results for the transport properties in unconventional superconductors and ferromagnetic systems with multiple broken symmetries. In Paper I and parts of Paper II we have studied tunneling transport between two non-unitary ferromagnetic spin-triplet superconductors, and found a novel interplay between ferromagnetism and superconductivity manifested in the Josephson effect as a spin- and charge-current in the absence of an applied voltage across the junction. The critical amplitudes of these currents can be adjusted by the relative magnetization direction on each side of the junction. Furthermore, in Paper II, we have found a way of controlling a spin-current between two ferromagnets with spin-orbit coupling. Paper III considers a junction consisting of a ferromagnet and a non-unitary ferromagnetic superconductor, and we show that the conductance spectra contains detailed information about the superconducting gaps and pairing symmetry of the Cooper-pairs. In the last paper we present a Monte Carlo study of an effective Hamiltonian describing orbital currents in the CuO2 layers of high-temperature superconductive cuprates. The model features two intrinsically anisotropic Ising models, coupled through an anisotropic next-nearest neighbor interaction, and an Ashkin-Teller nearest neighbor fourth order coupling. We have studied the specific heat anomaly, as well as the anomaly in the staggered magnetization associated with the orbital currents and its susceptibility. We have found that in a limited parameter regime, the specific heat anomaly is substantially suppressed, while the susceptibility has a non-analytical peak across the order-disorder transition. The model is therefore a candidate for describing the breakup of hidden order when crossing the pseudo-gap line on the under-doped side in the phase diagram of high-temperature superconductors. (Author) 64 refs., figs
The chirally rotated Schroedinger functional. Theoretical expectations and perturbative tests
Energy Technology Data Exchange (ETDEWEB)
Dalla Brida, Mattia [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany). John von Neumann-Inst. fuer Computing NIC; Sint, Stefan [Trinity College Dublin (Ireland). School of Mathematics; Vilaseca, Pol [Istituto Nazionale di Fisica Nucleare, Sezione di Roma (Italy)
2016-03-15
The chirally rotated Schroedinger functional (χSF) with massless Wilson-type fermions provides an alternative lattice regularization of the Schroedinger functional (SF), with different lattice symmetries and a common continuum limit expected from universality. The explicit breaking of flavour and parity symmetries needs to be repaired by tuning the bare fermion mass and the coefficient of a dimension 3 boundary counterterm. Once this is achieved one expects the mechanism of automatic O(a) improvement to be operational in the χSF, in contrast to the standard formulation of the SF. This is expected to significantly improve the attainable precision for step-scaling functions of some composite operators. Furthermore, the χSF offers new strategies to determine finite renormalization constants which are traditionally obtained from chiral Ward identities. In this paper we consider a complete set of fermion bilinear operators, define corresponding correlation functions and explain the relation to their standard SF counterparts. We discuss renormalization and O(a) improvement and then use this set-up to formulate the theoretical expectations which follow from universality. Expanding the correlation functions to one-loop order of perturbation theory we then perform a number of non-trivial checks. In the process we obtain the action counterterm coefficients to one-loop order and reproduce some known perturbative results for renormalization constants of fermion bilinears. By confirming the theoretical expectations, this perturbative study lends further support to the soundness of the χSF framework and prepares the ground for non-perturbative applications.
Theoretical studies of chemical reaction dynamics
Energy Technology Data Exchange (ETDEWEB)
Schatz, G.C. [Argonne National Laboratory, IL (United States)
1993-12-01
This collaborative program with the Theoretical Chemistry Group at Argonne involves theoretical studies of gas phase chemical reactions and related energy transfer and photodissociation processes. Many of the reactions studied are of direct relevance to combustion; others are selected they provide important examples of special dynamical processes, or are of relevance to experimental measurements. Both classical trajectory and quantum reactive scattering methods are used for these studies, and the types of information determined range from thermal rate constants to state to state differential cross sections.
The Function of Religiosity in Personal Development: Some Theoretical Remarks
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Tatjana Folieva
2014-12-01
Full Text Available Dwelling on a number of theoretical considerations bearing on the problem of the function of religiosity in personal development, the author specifi es the disciplines related to the study of the problem and formulates working defi nitions of the concepts of development, religiosity and norm. The situation in Russian science today gives priority to psychology of development and religion studies, as the former possesses a serious methodological and methodical basis while the latter, disposing of a unique mass of empiric material, provides broader context for studying religiosity and secures the link between its psychological study and its historical, sociological, henomenological etc. analysis. This approach will also be productive for theology, since psychology can occupy a special place within the system of ecclesiastical sciences as an applied discipline; however, its confessional” character should then fi nd expression not in the search for a religious basis, but in the study of phenomena belonging to the religious milieu. It is also suggested that religiosity should be considered as a ynamic, non-linear process which can be observed here and now and whose direction and specifi c character in the future can be prognosticated, albeit with a certain amount of reservation. Religiosity and development are two interconnected processes in which the person chooses the elements needed in his personal life for the self-regulation of the cognitive, aff ective and behavioral components. For this reason it seems rather diffi cult to determine the function of religiosity in the development of a personality.
Graph theoretical analysis of EEG functional connectivity during music perception.
Wu, Junjie; Zhang, Junsong; Liu, Chu; Liu, Dongwei; Ding, Xiaojun; Zhou, Changle
2012-11-05
The present study evaluated the effect of music on large-scale structure of functional brain networks using graph theoretical concepts. While most studies on music perception used Western music as an acoustic stimulus, Guqin music, representative of Eastern music, was selected for this experiment to increase our knowledge of music perception. Electroencephalography (EEG) was recorded from non-musician volunteers in three conditions: Guqin music, noise and silence backgrounds. Phase coherence was calculated in the alpha band and between all pairs of EEG channels to construct correlation matrices. Each resulting matrix was converted into a weighted graph using a threshold, and two network measures: the clustering coefficient and characteristic path length were calculated. Music perception was found to display a higher level mean phase coherence. Over the whole range of thresholds, the clustering coefficient was larger while listening to music, whereas the path length was smaller. Networks in music background still had a shorter characteristic path length even after the correction for differences in mean synchronization level among background conditions. This topological change indicated a more optimal structure under music perception. Thus, prominent small-world properties are confirmed in functional brain networks. Furthermore, music perception shows an increase of functional connectivity and an enhancement of small-world network organizations.
Theoretical aspects of studying the migration processes
Directory of Open Access Journals (Sweden)
Dilfuza Rasulova
2010-02-01
Full Text Available In conditions of continuous growth of population in Uzbekistan the issue of managing the labor migration processes is becoming more important. Effective coordination of migration processes requires comprehensive study of theory and methodology of labour migration, particularly considering cases of transition countries. The paper considers some theoretic concepts that seem important for understanding the mechanism of migration princesses, suggests practical recommendations for the associated decision-making.
Theoretical study of the NO beta system
Langhoff, Stephen R.; Partridge, Harry; Bauschlicher, Charles W., Jr.; Komornicki, Andrew
1991-01-01
A theoretical determination of the transition moment functions (TMFs) for the beta system of NO is presented. High levels of correlation treatment are required to show the changing degree of Rydberg character in the B2II with decreasing r values. The state-averaged complete-active-space self-consistent-field multireference configuration-interaction method is used for the determination. Previous lifetime measurements made with laser-induced fluorescence, varying between 2 and 0.85 microns, are discussed in terms of the calculated lifetimes for v-prime values 0-6, which vary from 2.12-1.17 microns. When larger r values are used for the transition moment function, the calculated lifetimes correlate with experimental lifetimes. The Einstein coefficients agree with experimental results, although limitations in the calibration of the spectrometer can account for systematic differences. The correlation with earlier experimental results suggests that radiative lifetimes are in the range of 1-2 microns.
Theoretical study of n-alkane adsorption on metal surfaces
DEFF Research Database (Denmark)
Morikawa, Yoshitada; Ishii, Hisao; Seki, Kazuhiko
2004-01-01
The interaction between n-alkane and metal surfaces has been studied by means of density-functional theoretical calculations within a generalized gradient approximation (GGA). We demonstrate that although the GGA cannot reproduce the physisorption energy well, our calculations can reproduce the e...
Theoretical study on single-molecule spectroscopy
Institute of Scientific and Technical Information of China (English)
SHAN Guang-cun; HUANG Wei
2006-01-01
The photon-by-photon approach for single molecule spectroscopy experiments utilizes the information carried by each detected photon and allows the measurements of conformational fluctuation with time resolution on a vast range of time scales,where each photon represents a data point.Here,we theoretically simulate the photon emission dynamics of a single molecule spectroscopy using the kinetic Monte Carlo algorithm to understand the underlying complex photon dynamic process of a single molecule.In addition,by following the molecular process in real time,the mechanism of complex biochemical reactions can be revealed.We hope that this theoretical study will serve as an introduction and a guideline into this exciting new field.
Ramos-Berdullas, Nicolás; Pérez-Juste, Ignacio; Van Alsenoy, Christian; Mandado, Marcos
2015-01-01
The suitability of implicitly dispersion-corrected functionals, namely the M06-2X, for the determination of interaction energies and electron polarization densities in adsorption studies of aromatic molecules on carbon allotropes surfaces is analysed by comparing the results with those obtained using explicit dispersion through Grimme's empirical corrections. Several models of increasing size for the graphene sheet together with one-dimensional curved carbon structures, (5,5), (6,6) and (7,7) armchair single-walled nanotubes, and two-dimensional curved carbon structures, C60 fullerene, have been considered as substrates in this work, whereas pyridine has been chosen as an example for the adsorbed aromatic molecule. Comparison with recent experimental estimations of the adsorption energy and calculations using periodic boundary conditions on a supercell of 72 carbon atoms indicates that a finite model containing ninety six carbon atoms (C96) approaches quite well the adsorption on a graphene sheet. Analysis of the interaction energy components reveals that the M06-2X functional accounts for most of the dispersion energy implicitly, followed far by wB97X and B3LYP, whereas B97 and BLYP do not differ too much from HF. It has been found that M06-2X corrects only the energy component associated to dispersion and leaves the rest, electrostatic, Pauli and induction "unaltered" with respect to the other DFT functionals investigated. Moreover, only the M06-2X functional reflects the effect of dispersion on the electron polarization density, whereas for the remaining functionals the polarization density does not differ too much from the HF density. This makes the former functional more suitable a priori for the calculation of electron density related properties in these adsorption complexes.
Vapor Sensing Theoretical Study on Optical Microcavities
Institute of Scientific and Technical Information of China (English)
ZHANG Le-xin; ZHANG Ran; LI Zhi-quan
2007-01-01
When the organic vapors absorbed to the surface of porous silicon(PS), capillary condensation takes place due to the porous structure of the PS layer, accordingly resulting in the effective refractive index changing. For PS multi-layer microcavities, the different resonant peaks shift in the reflectivity spectrum of porous silicon microcavities(PSMs). The optical sensing model is set up by applying Bruggeman effective medium approximation theory, capillary condensation process and transfer matrix theoretically analytical method of one-dimensional photonic crystals. At the same time, comprehensively researched on are the sensing characteristics of PSMs which are exposed to give concentration organic vapors. At last, made is the theoretical simulation for sensing model of the PSMs in case of saturation by using computer numerical calculation, and found is the linearity relation between the refractive index of organic solvent and the peak-shift. At the same time deduced is the peak-shift as a function of the concentration of ethanol vapors.
Imamura, Yutaka; Kamiya, Muneaki; Nakajima, Takahito
2016-03-01
We study spin-forbidden transitions of Os polypyridyl sensitizers by two-component relativistic time-dependent density functional theory with the spin-orbit interaction based on Tamm-Dancoff approximation. The absorption spectra, including spin-forbidden-transition peaks, for the Os complexes are reasonably reproduced in comparison with the experimental ones. The extension of the conjugated lengths in the Os complexes is investigated and found to be effective to enhance photo absorption for spin-allowed transitions as well as spin-forbidden ones. This study provides fruitful information for a design of new dyes in terms of conjugation lengths.
Institute of Scientific and Technical Information of China (English)
WANG Han-Lu; WANG Xue-Ye; WANG Ling; WANG Heng-Liang; LIU Ai-Hong
2007-01-01
Electronic properties, such as HOMO and LUMO energies, band gaps, ionization potential (IP) and electron affinity (EA) of 2,7- and 3,6-linked carbazole trimers, two conjugated oligomers with different linkages of carbazole, were studied by the density functional theory with Becke-Lee-Young-Parr composite exchange correlation functional (B3LYP). The absorption spectra of these compounds were also investigated by time-dependent density functional theory (TD-DFT) with 6-31G* basis set. The calculated results indicated that the HOMO and LUMO of the 2,7- and 3,6-linked carbazole trimers are both slightly destabilized on going from methyl substitution to sec-butyl substitution. Both IP and EA exhibit their good hole-transporting but poor electron-accepting ability. The presence of alkyl groups on the nitrogen atoms does not affect the intra-chain electronic delocalization along the molecular frame. Thus no significant effect on the band gap and absorption spectra of compounds has been found.
Theoretical pluralism in psychoanalytic case studies.
Willemsen, Jochem; Cornelis, Shana; Geerardyn, Filip M; Desmet, Mattias; Meganck, Reitske; Inslegers, Ruth; Cauwe, Joachim M B D
2015-01-01
The aim of this study is to provide an overview of the scientific activity of different psychoanalytic schools of thought in terms of the content and production of case studies published on ISI Web of Knowledge. Between March 2013 and November 2013, we contacted all case study authors included in the online archive of psychoanalytic and psychodynamic case studies (www.singlecasearchive.com) to inquire about their psychoanalytic orientation during their work with the patient. The response rate for this study was 45%. It appears that the two oldest psychoanalytic schools, Object-relations psychoanalysis and Ego psychology or "Classical psychoanalysis" dominate the literature of published case studies. However, most authors stated that they feel attached to two or more psychoanalytic schools of thought. This confirms that the theoretical pluralism in psychoanalysis stretches to the field of single case studies. The single case studies of each psychoanalytic school are described separately in terms of methodology, patient, therapist, or treatment features. We conclude that published case studies features are fairly similar across different psychoanalytic schools. The results of this study are not representative of all psychoanalytic schools, as some do not publish their work in ISI ranked journals.
Theoretical Study on Standing Wave Thermoacoustic Engine
Kalra, S.; Desai, K. P.; Naik, H. B.; Atrey, M. D.
Applications of thermoacoustic engines are not limited to driving pulse tube cryocoolers. The performance of a thermoacoustic engine is governed by various design parameters like type of resonator, stack geometry, frequency, type of working gas etc. and various operating parameters like heat input, charging pressure etc. It is very important to arrive at an optimum configuration of the engine for which a theoretical model is required. In the present work, a theoretical analysis, based on linear acoustic theory of a standing wave type half wavelength thermoacoustic engine is carried out using DeltaEC software. The system dimensions like length of resonator, stack, hot and cold heat exchangers are fixed with a helium-argon mixture as the working gas and a parallel plate type stack. Later on, two plate spacings, corresponding to helium-argon mixture and nitrogen gas, are used for carrying out analysis with helium, argon, nitrogen, carbon dioxide and helium-argon mixture as working gases of the system. The effect of charging pressure on the performance of the system is studied in terms of resonating frequency, onset temperature, pressure amplitude, acoustic power and efficiency. The conclusions derived from the analysis are reported in the paper.
Graph theoretical analysis of resting magnetoencephalographic functional connectivity networks
Directory of Open Access Journals (Sweden)
Lindsay eRutter
2013-07-01
Full Text Available Complex networks have been observed to comprise small-world properties, believed to represent an optimal organization of local specialization and global integration of information processing at reduced wiring cost. Here, we applied magnitude squared coherence to resting magnetoencephalographic time series in reconstructed source space, acquired from controls and patients with schizophrenia, and generated frequency-dependent adjacency matrices modeling functional connectivity between virtual channels. After configuring undirected binary and weighted graphs, we found that all human networks demonstrated highly localized clustering and short characteristic path lengths. The most conservatively thresholded networks showed efficient wiring, with topographical distance between connected vertices amounting to one-third as observed in surrogate randomized topologies. Nodal degrees of the human networks conformed to a heavy-tailed exponentially truncated power-law, compatible with the existence of hubs, which included theta and alpha bilateral cerebellar tonsil, beta and gamma bilateral posterior cingulate, and bilateral thalamus across all frequencies. We conclude that all networks showed small-worldness, minimal physical connection distance, and skewed degree distributions characteristic of physically-embedded networks, and that these calculations derived from graph theoretical mathematics did not quantifiably distinguish between subject populations, independent of bandwidth. However, post-hoc measurements of edge computations at the scale of the individual vertex revealed trends of reduced gamma connectivity across the posterior medial parietal cortex in patients, an observation consistent with our prior resting activation study that found significant reduction of synthetic aperture magnetometry gamma power across similar regions. The basis of these small differences remains unclear.
Kikkinides, E S; Monson, P A
2015-03-07
Building on recent developments in dynamic density functional theory, we have developed a version of the theory that includes hydrodynamic interactions. This is achieved by combining the continuity and momentum equations eliminating velocity fields, so the resulting model equation contains only terms related to the fluid density and its time and spatial derivatives. The new model satisfies simultaneously continuity and momentum equations under the assumptions of constant dynamic or kinematic viscosity and small velocities and/or density gradients. We present applications of the theory to spinodal decomposition of subcritical temperatures for one-dimensional and three-dimensional density perturbations for both a van der Waals fluid and for a lattice gas model in mean field theory. In the latter case, the theory provides a hydrodynamic extension to the recently studied dynamic mean field theory. We find that the theory correctly describes the transition from diffusive phase separation at short times to hydrodynamic behaviour at long times.
Theoretical Studies on Photoionization Cross Sections of Solid Gold
Institute of Scientific and Technical Information of China (English)
MA Xiao-Guang; SUN Wei-Guo; CHENG Yah-Song
2005-01-01
Accurate expression for photoabsorption (photoionization) cross sections of high density system proposed recently is used to study the photoionization of solid gold. The results show that the present theoretical photoionization cross sections have good agreement both in structure and in magnitude with the experimental results of gold crystal.The studies also indicate that both the real part ε'and the imaginary part ε" of the complex dielectric constant ε,and the dielectric influence function of a nonideal system have rich structures in low energy side with a range about 50 eV, and suggest that the influence of particle interactions of surrounding particles with the photoionized particle on the photoionization cross sections can be easily investigated using the dielectric influence function. The electron overlap effects are suggested to be implemented in the future studies to improve the accuracy of theoretical photoionization cross sections of a solid system.
Theoretical study of rock mass investigation efficiency
Energy Technology Data Exchange (ETDEWEB)
Holmen, Johan G.; Outters, Nils [Golder Associates, Uppsala (Sweden)
2002-05-01
The study concerns a mathematical modelling of a fractured rock mass and its investigations by use of theoretical boreholes and rock surfaces, with the purpose of analysing the efficiency (precision) of such investigations and determine the amount of investigations necessary to obtain reliable estimations of the structural-geological parameters of the studied rock mass. The study is not about estimating suitable sample sizes to be used in site investigations.The purpose of the study is to analyse the amount of information necessary for deriving estimates of the geological parameters studied, within defined confidence intervals and confidence level In other words, how the confidence in models of the rock mass (considering a selected number of parameters) will change with amount of information collected form boreholes and surfaces. The study is limited to a selected number of geometrical structural-geological parameters: Fracture orientation: mean direction and dispersion (Fisher Kappa and SRI). Different measures of fracture density (P10, P21 and P32). Fracture trace-length and strike distributions as seen on horizontal windows. A numerical Discrete Fracture Network (DFN) was used for representation of a fractured rock mass. The DFN-model was primarily based on the properties of an actual fracture network investigated at the Aespoe Hard Rock Laboratory. The rock mass studied (DFN-model) contained three different fracture sets with different orientations and fracture densities. The rock unit studied was statistically homogeneous. The study includes a limited sensitivity analysis of the properties of the DFN-model. The study is a theoretical and computer-based comparison between samples of fracture properties of a theoretical rock unit and the known true properties of the same unit. The samples are derived from numerically generated boreholes and surfaces that intersect the DFN-network. Two different boreholes are analysed; a vertical borehole and a borehole that is
Theoretical studies on aerosol agglomeration processes
Energy Technology Data Exchange (ETDEWEB)
Lehtinen, K.E.J. [VTT Energy, Espoo (Finland). Energy Use
1997-12-31
In this thesis, theoretical modeling of certain aerosol systems has been presented. At first, the aerosol general dynamic equation is introduced, along with a discretization routine for its numerical solution. Of the various possible phenomena affecting aerosol behaviour, this work is mostly focused on aerosol agglomeration. The fundamentals of aerosol agglomeration theory are thus briefly reviewed. The two practical applications of agglomeration studied in this thesis are flue gas cleaning using an electrical agglomerator and nanomaterial synthesis with a free jet reactor. In an electrical agglomerator the aerosol particles are charged and brought into an alternating electric field. The aim is to remove submicron particles from flue gases by collisions with larger particles before conventional gas cleaning devices that have a clear penetration window in the problematic 0.1-1{mu}m size range. A mathematical model was constructed to find out the effects of the different system parameters on the agglomerator`s performance. A crucial part of this task was finding out the collision efficiencies of particles of varying size and charge. The original idea was to use unipolar charging of the particles, and a laboratory scale apparatus was constructed for this purpose. Both theory and experiments clearly show that significant removal of submicron particles can not be achieved by such an arrangement. The theoretical analysis further shows that if the submicron particles and the large collector particles were charged with opposite polarity, significant removal of the submicron particles could be obtained. The second application of agglomeration considered in this thesis is predicting/controlling nanoparticle size in the gas-to-particle aerosol route to material synthesis. In a typical material reactor, a precursor vapor reacts to form molecules of the desired material. In a cooling environment, a particulate phase forms, the dynamics of which are determined by the rates of
Energy Technology Data Exchange (ETDEWEB)
Liang, Hong [Institute of Architecture and Engineering, Weifang University of Science and Technology, Weifang 262700 (China); Xu, Shunfu, E-mail: xushunfu2009@gmail.com [Institute of Architecture and Engineering, Weifang University of Science and Technology, Weifang 262700 (China); Department of Physics, Institute of Information Science and Engineering, Ocean University of China, Qingdao 266100 (China); Liu, Weihui [Department of Physics, Institute of Information Science and Engineering, Ocean University of China, Qingdao 266100 (China); Sun, Yueqiang; Liu, Xiangfa; Zheng, Xinqing; Li, Sen; Zhang, Qiang; Zhu, Ziliang; Zhang, Xiaochun; Dong, Chengguo [Institute of Architecture and Engineering, Weifang University of Science and Technology, Weifang 262700 (China); Li, Chun [Department of Physics, Institute of Information Science and Engineering, Ocean University of China, Qingdao 266100 (China); Yuan, Guang, E-mail: yuanguang@ouc.edu.cn [Department of Physics, Institute of Information Science and Engineering, Ocean University of China, Qingdao 266100 (China); Research Institute of Electronics, University of Shizuoka, Hamamasu 432-8011 (Japan); Mimura, Hitenori [Department of Physics, Institute of Information Science and Engineering, Ocean University of China, Qingdao 266100 (China)
2013-11-15
The impact of alkali-metal (Li/Na/Cs) adsorption on work function of fullerenes C{sub 60} and C{sub 70} was investigated by first-principles calculations. After adsorption, the work functions of fullerenes C{sub 60} and C{sub 70} decrease distinctly and vary linearly with the electronegativity of the alkali metal elements, and the positions where the alkali atoms are adsorbed considerably influence the work functions. On the contrary, a vacancy defect elevates the work functions of the fullerenes C{sub 60} and C{sub 70}. The variation in the work functions rests with variation in Fermi level (which are attributed to charge transfer) and variation in vacuum levels (which are attributed to the induced dipole moments). Moreover, alkali-metal adsorption can also improve the electric conductivity of a fullerene mixture of C{sub 60} and C{sub 70}.
Verevkin, Sergey P; Emel'yanenko, Vladimir N; Nagrimanov, Ruslan N
2016-12-15
Standard molar enthalpies of formation of 2- and 4-hydroxybenzamides were measured by combustion calorimetry. Vapor pressures of benzamide and 2-hydroxybenzamide were derived by the transpiration method. Standard molar enthalpies of sublimation or vaporization of these compounds at 298 K were obtained from vapor pressure temperature dependence. Thermochemical data on benzamides with hydroxyl, methyl, methoxy, amino, and amide substituents were collected, evaluated, and tested for internal consistency. The high-level G4 quantum-chemical method was used for mutual validation of the experimental and theoretical gas-phase enthalpies of formation. Sets of nearest-neighbor and non-nearest-neighbor interactions between substituents in the benzene ring have been evaluated. A simple incremental procedure has been suggested for a quick appraisal of the vaporization and gas-phase formation enthalpies of the substituted benzamides.
Studies In Theoretical High Energy Particle Physics
Energy Technology Data Exchange (ETDEWEB)
Keung, Wai Yee [Univ. of Illinois, Chicago, IL (United States)
2017-07-01
This is a final technical report for grant no. DE-SC0007948 describing research activities in theoretical high energy physics at University of Illinois at Chicago for the whole grant period from July 1, 2012 to March 31, 2017.
Directory of Open Access Journals (Sweden)
Sergey Uzhegov
2011-09-01
Full Text Available The current study examines how analysis of the Phenomenon of Plenty, paradox of economic underperformance of resource-rich nations, could benefit from theoretical and empirical application of suggested petroleum production function framework, basing on sample oil-abundant countries of the Commonwealth of Independent States, in particular Russia, Azerbaijan, and Kazakhstan. Proposed approach displays capacity of oil-economy production function to shed light on larger scope of theoretical issues. Empirical testing of suggested theoretical framework exhibited ability of proxied components of devised production function, capturing main metrics of the Phenomenon of Plenty and additionally factoring in corruption, to exert a strong impact on the majority of twelve principal macroeconomic indicators monitored by CIS supra-national institutions: with most pronounced influence on gross domestic product, industrial production, capital investments, and export to CIS countries.
Silva, Tânia B. E.; Pereira, Mariano A.; Malta, Valéria S.; Bento, Edson S.; San-Miguel, Miguel A.; Ziolli, Roberta L.; Martins, João B. L.; Sih, Andre; Taft, Carlton A.
A set of 30 cannabinoid metabolites has been investigated from a combination of electronic and chemometric methods. Density functional calculations have been carried out to obtain optimized geometries, energies, and selected molecular properties. These molecular descriptors take into account steric effects, electronic properties, and chemical reactivity. The use of statistical methods including principal component analysis (PCA), hierarchical cluster analysis (HCA) and nonhierarchical cluster analysis (K-means), nearest neighbor (KNN) and artificial neural networks (ANN) has enabled to classify the compounds into psychoactive, moderately psychoactive and psychoinactive groups in good agreement with experimental evidences.
THEORETICAL STUDY OF THREE-DIMENSIONAL NUMERICAL MANIFOLD METHOD
Institute of Scientific and Technical Information of China (English)
LUO Shao-ming; ZHANG Xiang-wei; L(U) Wen-ge; JIANG Dong-ru
2005-01-01
The three-dimensional numerical manifold method(NMM) is studied on the basis of two-dimensional numerical manifold method. The three-dimensional cover displacement function is studied. The mechanical analysis and Hammer integral method of three-dimensional numerical manifold method are put forward. The stiffness matrix of three-dimensional manifold element is derived and the dissection rules are given. The theoretical system and the numerical realizing method of three-dimensional numerical manifold method are systematically studied. As an example, the cantilever with load on the end is calculated, and the results show that the precision and efficiency are agreeable.
Theoretical Studies Of Small Boson Clusters
Chen, Y
2005-01-01
This work uses the DVR method to study the vibrational states of small boson clusters. With the adiabatic hyperspherical approximation, the lower and upper bounds of the bound states of the helium trimer are calculated. The first fully converged 3-dimensional basis set variational calculation for this system is carried out using Pekeris coordinates and the Laguerre basis functions. Two bound states are found for the system, as well as a third state which might be an Efimov state. The same method is used to study the bound states and resonance states of the neon trimer using a realistic potential, and proved to be efficient and accurate.
Experimental and theoretical studies of interactions between Si{7} clusters
Gynz-Rekowski, F. V.; Quester, W.; Dietsche, R.; Lim, D. C.; Bertram, N.; Fischer, T.; Ganteför, G.; Schach, M.; Nielaba, P.; Kim, Y. D.
2007-12-01
The possibility of using magic Si7 clusters to form a cluster material was studied experimentally and theoretically. In experiments Si7 clusters were deposited on carbon surfaces, and the electronic structure and chemical properties of the deposited clusters were measured using X-ray photoelectron spectroscopy (XPS). A non bulk-like electronic structure of Si7 was found in the Si 2p core level spectra. Si7 is suggested to form a more stable structure than the non-magic Si8 cluster and Si atoms upon deposition on carbon surfaces. Theoretically it was possible to study the interaction between the clusters without the effect of a surface. Density functional theory (DFT) calculations of potential curves of two free Si7 clusters approaching each other in various orientations hint at the formation of cluster materials rather than the fusion of clusters forming bulk-like structures.
Theoretical Study of a Spherical Plasma Focus
Ay, Yasar
A theoretical model is developed for two concentric electrodes spherical plasma focus device in order to investigate the plasma sheath dynamics, radiative emission, and the ion properties. The work focuses on the model development of the plasma sheath dynamics and its validation, followed by studying of the radiation effects and the beam-ion properties in such unique geometry as a pulsed source for neutrons, soft and hard x-rays, and electron and ion beams. Chapter 1 is an introduction on fusion systems including plasma focus. Chapter 2 is an extensive literature survey on plasma focus modeling and experiments including the various radiations and their mechanism. Chapter 3 details modeling and validation of the plasma sheath dynamics model with comparison between hydrogen, deuterium, tritium and deuterium-tritium mixture for the production of pulsed neutrons. Chapter 4 is a study of the radiative phase, in which neutron yield is investigated, as well as the predicted beam-ion properties. Chapter 5 summarizes and discusses the results. Chapter 6 provides concluding remarks and proposed future works. The phases of the developed model are the rundown phase I, rundown phase II, the reflected phase and a radiative phase. The rundown phase I starts immediately after the completion of the gas breakdown and ends when the current sheath reaches the equator point of the spherical shape. Then immediately followed by rundown phase II to start and it ends when the shock front hits the axis, which is the beginning of the reflected shock phase. Reflected shock front moves towards the incoming current sheath and meets it which is both the end of the reflected shock phase and the beginning of the radiative phase. After the reflected shock front and the current sheath meet, the current sheath continues to move radially inward by compressing the produced plasma column until it reaches the axis. Since the discharge current contains important information about the plasma dynamic
Institute of Scientific and Technical Information of China (English)
LIU Hongfei; JIA Tiekun; MIN Xinmin
2014-01-01
Density functional theory calculations were carried out to explore the potential energy surface (PES) associated with the gas-phase reaction of NiL2(L=SO3CH3) with acetone. The geometries and energies of the reactants, intermediates, products and transition states of the triplet ground potential energy surfaces of [Ni, O, C2, H4] were obtained at the B3LYP/6-311++G(d,p) levels in C,H,O atoms and B3LYP/Lanl2dz in Ni atom. It was found through our calculations that the decabonylation of acetaldehyde contains four steps including encounter complexation, C-C activation, aldehyde H-shift and nonreactive dissociation. The results revealed that C-C activation induced by NiL2(L=SO3CH3) led to the decarbonylation of acetaldehyde.
McDonald, William J.
In the present work density functional theory calculations were performed to explore the vibrational and electronic spectral changes associated with proton and electron transfer from the CuB center at the active site of cytochrome c oxidase that lead to the formation of either the PR or PM intermediates in the catalytic reduction of dioxygen to water. Furthermore, the thermodynamics of proton and electron transfer from the cross-linked histidine-tyrosine Cu B ligand were explored to assess the possible role of this ligand as a proton and/or electron donor during enzymatic turnover. Characteristic calculated cross-linked imidazole-phenolate and imidazole-phenoxyl radical vibrational frequencies and isotope shifts are in good agreement with the vibrational spectra of the PR and PM intermediates of the bo3 quinol oxidase from E. coli and R. sphaeroides and P. denitrificans suggesting that the Y244 (bovine numbering) is deprotonated in the PR intermediate, and is a tyrosyl radical in P M. Furthermore, using isodesmic reactions, the cross-linked phenol is found to be a significantly stronger acid than an unmodified phenol in the gas-phase, and likely in the inhomogeneous low-dielectric environment of the membrane bound enzyme, supporting the conclusion that the cross-linked tyrosine is a proton donor during enzymatic turnover. Time-dependent density functional theory calculations qualitatively reproduce the red-shift in the UV/visible absorption spectrum of a cross-linked imidazole-phenolate anion compared to the imidazole-phenol. Furthermore, the unique ˜500 nm absorption of a cross-linked imidazole-phenoxyl radical is correctly predicted using TDDFT and may be assigned as an imidazole-phenoxyl radical pi-to-pi* transition. Furthermore, this absorption is predicted in the spectrum of a Cu2+-imidazole-phenoxyl biradical model.
Theoretical Studies in Elementary Particle Physics
Energy Technology Data Exchange (ETDEWEB)
Collins, John C.; Roiban, Radu S
2013-04-01
This final report summarizes work at Penn State University from June 1, 1990 to April 30, 2012. The work was in theoretical elementary particle physics. Many new results in perturbative QCD, in string theory, and in related areas were obtained, with a substantial impact on the experimental program.
Voltammetry at porous electrodes: A theoretical study
Barnes, Edward O; Li, Peilin; Compton, Richard G
2014-01-01
Theory is presented to simulate both chronoamperometry and cyclic voltammetry at porous electrodes fabricated by means of electro-deposition around spherical templates. A theoretical method to extract heterogeneous rate constants for quasireversible and irreversible systems is proposed by the approximation of decoupling of the diffusion within the porous electrode and of bulk diffusion to the electrode surface.
Theoretic Study of CⅡ Recombination Line
Institute of Scientific and Technical Information of China (English)
彭永伦; 王民盛; 韩小英; 李家明
2004-01-01
Using the R-matrix method, we carry out theoretical calculations for recombination line λ 8794 A(3d'-3p') of CⅡ, which is important to estimate the abundances of carbon in planetary nebulae. Our calculations are based on three sets of target orbital basis, through which we elucidate the electron correlation and static polarization effects in the dielectronic recombination processes.
Characterization of Linearly Separable Boolean Functions: A Graph-Theoretic Perspective.
Rao, Yanyi; Zhang, Xianda
2016-04-05
In this paper, we present a novel approach for studying Boolean function in a graph-theoretic perspective. In particular, we first transform a Boolean function f of n variables into an induced subgraph Hf of the n-dimensional hypercube, and then, we show the properties of linearly separable Boolean functions on the basis of the analysis of the structure of Hf. We define a new class of graphs, called hyperstar, and prove that the induced subgraph Hf of any linearly separable Boolean function f is a hyperstar. The proposal of hyperstar helps us uncover a number of fundamental properties of linearly separable Boolean functions in this paper.
Dai, Fei; Fan, Xiangru; Stratton, Gunnar R; Bellona, Christopher L; Holsen, Thomas M; Crimmins, Bernard S; Xia, Xiaoyan; Mededovic Thagard, Selma
2016-05-05
A novel electrical discharge plasma reactor configuration with and without iron ions was evaluated for the degradation of 0.02 mM Bisphenol A (BPA). The pseudo-first-order reaction rate constant calculated for the plasma treatment of BPA with a stainless steel electrode in the presence of dissolved ferrous ion (Fe(2+)) salts (termed plasma/Fenton treatment) was higher than in the plasma treatment in the absence of iron salts. At the optimal ferrous ion concentration, longer plasma treatment times resulted in higher BPA degradation rates, likely due to increased hydroxyl (OH) radical concentration formed through the decomposition of H2O2. Replacing the stainless steel with a carbon steel grounded electrode resulted in the release of iron ions from the carbon steel thereby increasing the rate of BPA removal and eliminating the need for iron salts. After the plasma/Fenton treatment, >97% of the residual iron salts were removed by coagulation/flocculation/sedimentation. Byproduct identification coupled with density functional theory (DFT) calculations confirmed that OH radical attack on BPA's hydroxyl group is the primary pathway for byproduct formation. Copyright © 2016 Elsevier B.V. All rights reserved.
Energy Technology Data Exchange (ETDEWEB)
Dai, Fei, E-mail: daif@clarkson.edu [Department of Civil and Environmental Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States); Fan, Xiangru, E-mail: fanx@clarkson.edu [Department of Chemical and Biomolecular Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States); Stratton, Gunnar R., E-mail: strattgr@clarkson.edu [Department of Chemical and Biomolecular Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States); Bellona, Christopher L., E-mail: cbellona@clarkson.edu [Department of Civil and Environmental Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States); Department of Civil and Environmental Engineering, 1500 Illinois St., Colorado School of Mines, Golden, 80401 CO (United States); Holsen, Thomas M., E-mail: tholsen@clarkson.edu [Department of Civil and Environmental Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States); Crimmins, Bernard S., E-mail: bcrimmin@clarkson.edu [Department of Civil and Environmental Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States); Xia, Xiaoyan, E-mail: xiax@clarkson.edu [Department of Civil and Environmental Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States); Mededovic Thagard, Selma, E-mail: smededov@clarkson.edu [Department of Chemical and Biomolecular Engineering, 8 Clarkson Avenue, Clarkson University, Potsdam, 13699 NY (United States)
2016-05-05
Highlights: • Combining the Fenton reaction with the plasma treatment reduces Bisphenol A concentration below the detection limit within 30 min. • Carbon steel electrode in the plasma reactor can be used as a source of iron ions. • OH radical attack on Bisphenol A is the primary pathway for byproduct formation. - Abstract: A novel electrical discharge plasma reactor configuration with and without iron ions was evaluated for the degradation of 0.02 mM Bisphenol A (BPA). The pseudo-first-order reaction rate constant calculated for the plasma treatment of BPA with a stainless steel electrode in the presence of dissolved ferrous ion (Fe{sup 2+}) salts (termed plasma/Fenton treatment) was higher than in the plasma treatment in the absence of iron salts. At the optimal ferrous ion concentration, longer plasma treatment times resulted in higher BPA degradation rates, likely due to increased hydroxyl (OH) radical concentration formed through the decomposition of H{sub 2}O{sub 2}. Replacing the stainless steel with a carbon steel grounded electrode resulted in the release of iron ions from the carbon steel thereby increasing the rate of BPA removal and eliminating the need for iron salts. After the plasma/Fenton treatment, >97% of the residual iron salts were removed by coagulation/flocculation/sedimentation. Byproduct identification coupled with density functional theory (DFT) calculations confirmed that OH radical attack on BPA’s hydroxyl group is the primary pathway for byproduct formation.
Directory of Open Access Journals (Sweden)
Imanelakehal
2016-05-01
Full Text Available Complex of cerium (III with (E-N-benzylidene-4-methoxyaniline is synthesized through a one-pot three-componentreaction from aromatical dehyde, aromatic amine and the CeCl3· 7 H2O, as an efficient catalyst. This cerium(IIIcom- plexis characterized by IR, 1H, and 13 CNMR-spectros copy and mass-spectraldata. Molecular structure, Mullikan charges, thermodynamic parameters; vibrational frequencies and intensities were calculated by Density Functional theory methods (B3LYP,B3PW91,mPW1PW91 and PBEPBE using the SDD basis set. The comparison between the calculated and experimental data inorder to attain the best quality and to predict the structure, the best perfor-mance in the vibration spectra perfected of the title compound,we have found that the harmonic vibration computed are in a good agreement with the observed in IRspectrum, for closest match we calculated optimal scaling factors can recommend for the IR spectral future predictions for unknown compounds of this class. In order to better comparison, we also root meansqu are values of the experimental and calculated IR bands are 16.64,16.64,17.45,17.66 and the mean absolute percentage error values are1.33,1.39,1.40, and 1.5forB3LYP, B3PW91,mPW1PW91, and PBEPBE methods respectively
Theoretical study on stability of hybrid bilayers
Silva, Thiago S.; de Lima Bernardo, Bertúlio; Azevedo, Sèrgio
2015-04-01
Motivated by the recent experimental realization of the hybrid nanostructure of graphene and boron nitride (h-BN) sheet, and studies of gap modulation by strain, we use first principles calculations based on density functional theory to investigate the effects of strain in hybrid bilayers composed of two monolayers of graphene with a nanodomain of {{B}3}{{N}3}. The calculations were made with two different approximations for the functional exchange-correlation, GGA and VDW-DF. We investigate the modification in the electronic structure and structural properties of various configurations of the hybrid bilayers. Among the configurations, those with Bernal stacking are found to be more stable when compared to the others. Studies of the compressive strain influence were made only in the structure that has been shown to be the most stable. We have found that the two approximations used in the calculations exhibit the same results for the electronic properties of all structures. The opening of the energy gap due to strain was possible in the calculations by using the GGA approximation, but the same does not happen in the calculations using the VDW-DF approximation. Our analysis shows that the VDW-DF approximation is better suited for studies involving surfaces.
Theoretical Studies of Solids under Extreme Conditions.
1983-12-01
C. Pattnaik, Phys. Rev. 1327, 3987 (1983). 9. M. E. Schabes , J. L. Fry and P. C. Pattnaik, Bull. 4I. Phys. Soc. 29, 76 (1984). 10. C. M. Varma et al...phonon interactions in transition metals," P. C. Pattnaik, M. E. Schabes and J. L. Fry,to be submitted to The Physical Review. 10. "A Study of the linear...C. Pattnaik, J. L. Fry and M. E. Schabes . 13. "Positron work functions in metallic alloys," P. C. Pattnaik and G. Fletcher (to be submitted to The
Sustainable Nanotechnology: Opportunities and Challenges for Theoretical/Computational Studies.
Cui, Qiang; Hernandez, Rigoberto; Mason, Sara E; Frauenheim, Thomas; Pedersen, Joel A; Geiger, Franz
2016-08-04
For assistance in the design of the next generation of nanomaterials that are functional and have minimal health and safety concerns, it is imperative to establish causality, rather than correlations, in how properties of nanomaterials determine biological and environmental outcomes. Due to the vast design space available and the complexity of nano/bio interfaces, theoretical and computational studies are expected to play a major role in this context. In this minireview, we highlight opportunities and pressing challenges for theoretical and computational chemistry approaches to explore the relevant physicochemical processes that span broad length and time scales. We focus discussions on a bottom-up framework that relies on the determination of correct intermolecular forces, accurate molecular dynamics, and coarse-graining procedures to systematically bridge the scales, although top-down approaches are also effective at providing insights for many problems such as the effects of nanoparticles on biological membranes.
Ghigo, Giovanni; Maranzana, Andrea; Tonachini, Glauco
2015-10-01
We report the results of a DFT study of the border oxidation by (1) Δg O2 of molecular models of armchair graphene nanoribbons (a-GNRs). The aim of this work is to propose a new method, as an alternative or complementary method to the tuning of the size, to modify the electronic properties of a-GNRs. Here, we investigate modification of the HOMO and LUMO energies, which are some of the most important parameters to be controlled in the design of organic electronic devices. We study the oxidation reaction mechanism of medium-size polycyclic aromatic hydrocarbons, mimicking the stiffness and reactivity of a-GNRs. Thermodynamics and kinetics indicate that the reaction should bring about a decoration of the borders with vicinal dialdehyde groups. We also study the effect of this oxidation on the HOMO and LUMO energies of two series of molecular models of a-GNRs with increasing lengths. The results suggest that the oxidized a-GNRs should present LUMO energies lowered by 0.3-0.5 eV with respect to the original material, whereas the HOMO energies are barely lowered.
Theoretical study of pair density wave superconductors
Zheng, Zhichao
In conventional superconductors, the Cooper pairs are formed from quasiparticles. We explore another type of superconducting state, a pair density wave (PDW) order, which spontaneously breaks some of the translational and point group symmetries. In a PDW superconductor, the order parameter is a periodic function of the center-of-mass coordinate, and the spatial average value of the superconducting order parameter vanishes. In the early 1960s, following the success of the BCS theory of superconductivity, Fulde and Ferrell and Larkin and Ovchinnikov (FFLO) developed theories of inhomogeneous superconducting states. Because of this Zeeman splitting in a magnetic field, the Cooper pairs having a nonzero center-of-mass momentum are more stable than the normal pairing, leading to the FFLO state. Experiments suggest possible occurrence of the FFLO state in the heavy-fermion compound CeCoIn5, and in quasi-low-dimensional organic superconductors. FFLO phases have also been argued to be of importance in understanding ultracold atomic Fermi gases and in the formation of color superconductivity in high density quark matter. In all Fermi superfluids known at the present time, Cooper pairs are composed of particles with spin 1/2. The spin component of a pair wave function can be characterized by its total spin S = 0 (singlet) and S = 1 (triplet). In the discovered broken inversion superconductors CePt3Si, Li2Pt3B, and Li2Pd3B, the magnetic field leads to novel inhomogeneous superconducting states, namely the helical phase and the multiple-q phase. Its order parameter exhibits periodicity similar to FFLO phase, and the consequences of both phases are same: the enhancement of transition temperature as a function of magnetic field. We have studied the PDW phases in broken parity superconductors with vortices included. By studying PDW vortex states, we find the usual Abrikosov vortex solution is unstable against a new solution with fractional vortex pairs. We have also studied the
Theoretical Studies of Substitutionally Doped Single-Walled Nanotubes
Directory of Open Access Journals (Sweden)
Charles See Yeung
2010-01-01
Full Text Available The rich chemistry of single-walled carbon nanotubes (SWCNTs is enhanced by substitutional doping, a process in which a single atom of the nanotube sidewall is replaced by a heteroatom. These so-called heteroatom-substituted SWCNTs (HSWCNTs exhibit unique chemical and physical properties not observed in their corresponding undoped congeners. Herein, we present theoretical studies of both main group element and transition metal-doped HSWCNTs. Within density functional theory (DFT, we discuss mechanistic details of their proposed synthesis from vacancy-defected SWCNTs and describe their geometric and electronic properties. Additionally, we propose applications for these nanomaterials in nanosensing, nanoelectronics, and nanocatalysis.
Theoretical Study of the Diastereofacial Isomers of Aldrin and Dieldrin
Directory of Open Access Journals (Sweden)
Zoran Zdravkovski
2006-02-01
Full Text Available The Diels-Alder reaction of hexachlorocyclopentadiene with norbornadiene givesaldrin but theoretically three other diastereofacial isomers are possible. On oxidation theseisomers can generate eight adducts one of which is known as dieldrin. All these, as well asthe corresponding reactions with hexafluorocyclopenadiene were studied by semiempirical(AM1 and PM3 and hybrid density functional (B3LYP methods. Besides the energy levels,the transition states were calculated for the reactions leading to the diastereofacial isomers ofaldrin, which indicate that aldrin is the favored product of the reaction both fromthermodynamic and kinetic point of view.
Theoretical studies on nitrogen rich energetic azoles.
Ghule, Vikas Dasharath; Sarangapani, Radhakrishnan; Jadhav, Pandurang M; Tewari, Surya P
2011-06-01
Different nitro azole isomers based on five membered heterocyclics were designed and investigated using computational techniques in order to find out the comprehensive relationships between structure and performances of these high nitrogen compounds. Electronic structure of the molecules have been calculated using density functional theory (DFT) and the heat of formation has been calculated using the isodesmic reaction approach at B3LYP/6-31G* level. All designed compounds show high positive heat of formation due to the high nitrogen content and energetic nitro groups. The crystal densities of these energetic azoles have been predicted with different force fields. All the energetic azoles show densities higher than 1.87 g/cm(3). Detonation properties of energetic azoles are evaluated by using Kamlet-Jacobs equation based on the calculated densities and heat of formations. It is found that energetic azoles show detonation velocity about 9.0 km/s, and detonation pressure of 40GPa. Stability of the designed compounds has been predicted by evaluating the bond dissociation energy of the weakest C-NO(2) bond. The aromaticity using nucleus independent chemical shift (NICS) is also explored to predict the stability via delocalization of the π-electrons. Charge on the nitro group is used to assess the impact sensitivity in the present study. Overall, the study implies that all energetic azoles are found to be stable and expected to be the novel candidates of high energy density materials (HEDMs).
A Combined Theoretical and Experimental Study for Silver Electroplating
Liu, Anmin; Ren, Xuefeng; An, Maozhong; Zhang, Jinqiu; Yang, Peixia; Wang, Bo; Zhu, Yongming; Wang, Chong
2014-01-01
A novel method combined theoretical and experimental study for environmental friendly silver electroplating was introduced. Quantum chemical calculations and molecular dynamic (MD) simulations were employed for predicting the behaviour and function of the complexing agents. Electronic properties, orbital information, and single point energies of the 5,5-dimethylhydantoin (DMH), nicotinic acid (NA), as well as their silver(I)-complexes were provided by quantum chemical calculations based on density functional theory (DFT). Adsorption behaviors of the agents on copper and silver surfaces were investigated using MD simulations. Basing on the data of quantum chemical calculations and MD simulations, we believed that DMH and NA could be the promising complexing agents for silver electroplating. The experimental results, including of electrochemical measurement and silver electroplating, further confirmed the above prediction. This efficient and versatile method thus opens a new window to study or design complexing agents for generalized metal electroplating and will vigorously promote the level of this research region.
Theoretical Studies of Homogeneous Catalysts Mimicking Nitrogenase
Directory of Open Access Journals (Sweden)
Alessandra Magistrato
2011-01-01
Full Text Available The conversion of molecular nitrogen to ammonia is a key biological and chemical process and represents one of the most challenging topics in chemistry and biology. In Nature the Mo-containing nitrogenase enzymes perform nitrogen ‘fixation’ via an iron molybdenum cofactor (FeMo-co under ambient conditions. In contrast, industrially, the Haber-Bosch process reduces molecular nitrogen and hydrogen to ammonia with a heterogeneous iron catalyst under drastic conditions of temperature and pressure. This process accounts for the production of millions of tons of nitrogen compounds used for agricultural and industrial purposes, but the high temperature and pressure required result in a large energy loss, leading to several economic and environmental issues. During the last 40 years many attempts have been made to synthesize simple homogeneous catalysts that can activate dinitrogen under the same mild conditions of the nitrogenase enzymes. Several compounds, almost all containing transition metals, have been shown to bind and activate N2 to various degrees. However, to date Mo(N2(HIPTN3N with (HIPTN3N= hexaisopropyl-terphenyl-triamidoamine is the only compound performing this process catalytically. In this review we describe how Density Functional Theory calculations have been of help in elucidating the reaction mechanisms of the inorganic compounds that activate or fix N2. These studies provided important insights that rationalize and complement the experimental findings about the reaction mechanisms of known catalysts, predicting the reactivity of new potential catalysts and helping in tailoring new efficient catalytic compounds.
Computing FIRST and FOLLOW Functions for Feature-Theoretic Grammars
Trujillo, A
1994-01-01
This paper describes an algorithm for the computation of FIRST and FOLLOW sets for use with feature-theoretic grammars in which the value of the sets consists of pairs of feature-theoretic categories. The algorithm preserves as much information from the grammars as possible, using negative restriction to define equivalence classes. Addition of a simple data structure leads to an order of magnitude improvement in execution time over a naive implementation.
Theoretical study of conjugated porphyrin polymers
DEFF Research Database (Denmark)
Pedersen, T.G.; Lynge, T.B.; Kristensen, P.K.
2005-01-01
The optical gap of conjugated triply linked porphyrin chains is exceptionally low (similar to 0.5 eV). Hence, such chains are candidates for organic infrared detectors and solar cells harvesting the infrared part of the solar spectrum. However, a low exciton binding energy is required for these a......The optical gap of conjugated triply linked porphyrin chains is exceptionally low (similar to 0.5 eV). Hence, such chains are candidates for organic infrared detectors and solar cells harvesting the infrared part of the solar spectrum. However, a low exciton binding energy is required...... for these applications. From a theoretical analysis of excitons in long metalloporphyrin chains, we demonstrate that the binding energy is much lower than in usual conjugated polymers. Our calculated absorption spectra are in good agreement with measurements. (c) 2004 Elsevier B.V. All rights reserved....
Theoretical study on spherical proton emission
Institute of Scientific and Technical Information of China (English)
无
2009-01-01
The proton radioactivity half-lives of spherical proton emitters are investigated within a generalized liquid drop model(GLDM),including the proximity effects between nuclei in a neck and the mass and charge asymmetry.The penetrability is calculated in the WKB approximation and the assault frequency is estimated by the quantum mechanism method considering the structure of the parent nucleus.The spectroscopic factor is taken into account in half-life calculation,which is obtained by employing the relativistic mean field(RMF) theory.The half-lives within the GLDM are compared with the experimental data and other theoretical values.The results show that the GLDM works quite well for spherical proton emitters when the assault frequency is estimated by the quantum mechanical method and the spectroscopic factor is considered.
Theoretical study on spherical proton emission
Institute of Scientific and Technical Information of China (English)
ZHANG HongFei; WANG YongJia; DONG JianMin; LI JunQing
2009-01-01
The proton radioactivity half-lives of spherical proton emitters are investigated within a generalized liquid drop model (GLDM),including the proximity effects between nuclei in a neck and the mass and charge asymmetry.The penetrability is calculated in the WKB approximation and the assault frequency is estimated by the quantum mechanism method considering the structure of the parent nucleus.The spectroscopic factor is taken into account in half-life calculation,which is obtained by employing the relativistic mean field (RMF) theory.The half-lives within the GLDM are compared with the experimental data and other theoretical values.The results show that the GLDM works quite well for spherical proton emitters when the assault frequency is estimated by the quantum mechanical method and the spectroscopic factor is considered.
Theoretical Studies in Percolation and Polymer Theory
Wu, Kang
We study the theta points for the self-avoiding walk (SAW) and the self-avoiding trail (SAT). In a small cell real space renormalization group study on a model that includes self-attracting SAW's (SASAW) and self-attracting SAT's (SASAT) as special cases, we find distinct fixed points for the SASAW and SASAT collapse transitions, and so conclude that these transitions are in different universality classes. A percolation model, which we call bond percolation on antipercolation clusters (BPAPC), is introduced. A mapping between BPAPC and the diluted alternating Potts model (DAPM) is established. We solve the DAPM in the Bethe cluster approximation and obtain the static critical exponents beta = 1 and gamma = 1. The approximate phase diagram for arbitrary coordination number z is also constructed. In our Monte Carlo simulations of kinetic antipercolation, we observe growth oscillations that have no analog in regular percolation. A mean field theory that explains the existence of these oscillations is presented. The result of our simulations suggests that kinetic antipercolation may be in the same universality class as kinetic percolation. We introduce a dynamic fuse model for the damage done to a current-carrying polycrystalline metal thin film by electromigration. We determine the exact scaling behavior of the crack tip velocity for a single crack oriented perpendicularly to the direction of the ambient current. For any value of the initial density of defects, the mean failure time is to an excellent approximation proportional to the average length of the shortest path across the film in a certain metric. This conclusion is supported by our simulations and by analytical work based on a variational formulation of our problem. The Green's function formulation (GFF) is obtained for a random resistor network. The GFF yields a linear system equivalent to Kirchhoff's laws but with a smaller number of variables. We present the technical details of solving the GFF linear
Theoretical study of pulsed microwave discharge in nitrogen
Energy Technology Data Exchange (ETDEWEB)
Bonaventura, Z; Trunec, D; Mesko, M; Vasina, P; Kudrle, V [Department of Physical Electronics, Faculty of Science, Masaryk University, Kotlarska 2, 611 37 Brno (Czech Republic)
2005-11-15
A pulsed microwave discharge burning in pure nitrogen was studied theoretically. The time-dependent Boltzmann equation for electrons was solved numerically in multi-term approximation. It was assumed that the discharge was ignited by a 100 kW microwave (f = 9.4 GHz) pulses with 2.5 {mu}s duration; the repetition frequency was 400 Hz. It was shown that the electron distribution function approaches very quickly the steady state distribution function after a change of the amplitude of electric field intensity. The steady state time averaged values of electron mean energy, diffusion and rate coefficients and drift velocity were calculated for different values of electric field intensity. With these values the actual values of electric field intensity from a previous experiment were determined from the measured time dependence of electron concentration. The calculated values were compared with previous experimental results.
Theoretical Studies of Defects in Tetrahedral Semiconductors.
1980-08-01
within 5(E)=-tan-lf ImD(E) ReDE )l . 18) the band continua, we write Eq. (8) in the form It follows that ,5rE) goes through an odd multiple 1- 6 1(E...an atom from "h. The use of the FHT resulted in a very accurate determination of the Green’s-function matrix ele- _____- ments on an energy mesh ...spaced by 0.07 eV. This ,, mesh was found dense enough to allow interpolation , I ’or intermediate energy values when needed. The 2:- / Green’s-function
Exploring theoretical functions of corpus data in teaching translation
Directory of Open Access Journals (Sweden)
Éric Poirier
2016-06-01
Full Text Available As language referential data banks, corpora are instrumental in the exploration of translation solutions in bilingual parallel texts or conventional usages of source or target language in monolingual general or specialized texts. These roles are firmly rooted in translation processes, from analysis and interpretation of source text to searching for an acceptable equivalent and integrating it into the production of the target text. Provided the creative and not the conservative way be taken, validation or adaptation of target text in accordance with conventional usages in the target language also benefits from corpora. Translation teaching is not exploiting this way of translating that is common practice in the professional translation markets around the world. Instead of showing what corpus tools can do to translation teaching, we start our analysis with a common issue within translation teaching and show how corpus data can help to resolve it in learning activities in translation courses. We suggest a corpus-driven model for the interpretation of ‘business’ as a term and as an item in complex terms based on source text pattern analysis. This methodology will make it possible for teachers to explain and justify interpretation rules that have been defined theoretically from corpus data. It will also help teachers to conceive and non-subjectively assess practical activities designed for learners of translation. Corpus data selected for the examples of rule-based interpretations provided in this paper have been compiled in a corpus-driven study (Poirier, 2015 on the translation of the noun ‘business’ in the field of specialized translation in business, economics, and finance from English to French. The corpus methodology and rule-based interpretation of senses can be generalized and applied in the definition of interpretation rules for other language pairs and other specialized simple and complex terms. These works will encourage the
THEORETICAL STUDY ON ELECTRONIC STRUCTURES AND ...
African Journals Online (AJOL)
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method and density function theory (DFT) at B3LYP/6-31G(d) level. ... and the increase in the number of thiophene rings in the derivatives lead to the decrease ... At the same time, the first absorptions in the electronic spectra and the stretching ...
Experimental and Theoretical Study on Pyrolysis of Isopsoralen
Institute of Scientific and Technical Information of China (English)
Jiu-zhong Yang; Feng Zhang; Liang-yuan Jia; Li-dong Zhang; Fei Qi; Hai-yan Fan; Ji-bao Cai
2012-01-01
The pyrolysis of isopsoralen was studied by synchrotron vacuum ultraviolet photoionization mass spectrometry at low pressure.The pyrolysis products were detected at different photon energies,the ratios of products to precursor were measured at various pyrolysis temperatures.The experimental results demonstrate that the main pyrolysis products are primary CO and sequential CO elimination products (C10H6O2 and C9H6O).The decomposition channels of isopsoralen were also studied by the density functional theory,then rate constants for competing pathways were calculated by the transition state theory.The dominant decomposition channels of isopsoralen and the molecular structures for corresponding products were identified bv combined experimental and theoretical studies.
Theoretical Studies of Nanoclusters (Briefing Charts)
2015-07-23
representation of actual NP surface? • Reaction enthalpies and barriers for – chemisorption of NH3 – fragmentation of chemisorbed NH3 – formation of H2...suspended or dissolved in ionic liquids - surface-functionalized NPs can be dispersed in variety of liquids hydrocarbons , ILs, polar solvents...distribution unlimited. • DFT calculations (M06/6-311++G(d,p)) used to identify surface species and reactions leading to their formation. • Al80
Theoretical studies of potential energy surfaces and computational methods
Energy Technology Data Exchange (ETDEWEB)
Shepard, R. [Argonne National Laboratory, IL (United States)
1993-12-01
This project involves the development, implementation, and application of theoretical methods for the calculation and characterization of potential energy surfaces involving molecular species that occur in hydrocarbon combustion. These potential energy surfaces require an accurate and balanced treatment of reactants, intermediates, and products. This difficult challenge is met with general multiconfiguration self-consistent-field (MCSCF) and multireference single- and double-excitation configuration interaction (MRSDCI) methods. In contrast to the more common single-reference electronic structure methods, this approach is capable of describing accurately molecular systems that are highly distorted away from their equilibrium geometries, including reactant, fragment, and transition-state geometries, and of describing regions of the potential surface that are associated with electronic wave functions of widely varying nature. The MCSCF reference wave functions are designed to be sufficiently flexible to describe qualitatively the changes in the electronic structure over the broad range of geometries of interest. The necessary mixing of ionic, covalent, and Rydberg contributions, along with the appropriate treatment of the different electron-spin components (e.g. closed shell, high-spin open-shell, low-spin open shell, radical, diradical, etc.) of the wave functions, are treated correctly at this level. Further treatment of electron correlation effects is included using large scale multireference CI wave functions, particularly including the single and double excitations relative to the MCSCF reference space. This leads to the most flexible and accurate large-scale MRSDCI wave functions that have been used to date in global PES studies.
Theoretical & Experimental Studies of Elementary Particles
Energy Technology Data Exchange (ETDEWEB)
McFarland, Kevin
2012-10-04
Abstract High energy physics has been one of the signature research programs at the University of Rochester for over 60 years. The group has made leading contributions to experimental discoveries at accelerators and in cosmic rays and has played major roles in developing the theoretical framework that gives us our ``standard model'' of fundamental interactions today. This award from the Department of Energy funded a major portion of that research for more than 20 years. During this time, highlights of the supported work included the discovery of the top quark at the Fermilab Tevatron, the completion of a broad program of physics measurements that verified the electroweak unified theory, the measurement of three generations of neutrino flavor oscillations, and the first observation of a ``Higgs like'' boson at the Large Hadron Collider. The work has resulted in more than 2000 publications over the period of the grant. The principal investigators supported on this grant have been recognized as leaders in the field of elementary particle physics by their peers through numerous awards and leadership positions. Most notable among them is the APS W.K.H. Panofsky Prize awarded to Arie Bodek in 2004, the J.J. Sakurai Prizes awarded to Susumu Okubo and C. Richard Hagen in 2005 and 2010, respectively, the Wigner medal awarded to Susumu Okubo in 2006, and five principal investigators (Das, Demina, McFarland, Orr, Tipton) who received Department of Energy Outstanding Junior Investigator awards during the period of this grant. The University of Rochester Department of Physics and Astronomy, which houses the research group, provides primary salary support for the faculty and has waived most tuition costs for graduate students during the period of this grant. The group also benefits significantly from technical support and infrastructure available at the University which supports the work. The research work of the group has provided educational opportunities
Theoretical Studies of Hydrogen Storage Alloys.
Energy Technology Data Exchange (ETDEWEB)
Jonsson, Hannes
2012-03-22
Theoretical calculations were carried out to search for lightweight alloys that can be used to reversibly store hydrogen in mobile applications, such as automobiles. Our primary focus was on magnesium based alloys. While MgH{sub 2} is in many respects a promising hydrogen storage material, there are two serious problems which need to be solved in order to make it useful: (i) the binding energy of the hydrogen atoms in the hydride is too large, causing the release temperature to be too high, and (ii) the diffusion of hydrogen through the hydride is so slow that loading of hydrogen into the metal takes much too long. In the first year of the project, we found that the addition of ca. 15% of aluminum decreases the binding energy to the hydrogen to the target value of 0.25 eV which corresponds to release of 1 bar hydrogen gas at 100 degrees C. Also, the addition of ca. 15% of transition metal atoms, such as Ti or V, reduces the formation energy of interstitial H-atoms making the diffusion of H-atoms through the hydride more than ten orders of magnitude faster at room temperature. In the second year of the project, several calculations of alloys of magnesium with various other transition metals were carried out and systematic trends in stability, hydrogen binding energy and diffusivity established. Some calculations of ternary alloys and their hydrides were also carried out, for example of Mg{sub 6}AlTiH{sub 16}. It was found that the binding energy reduction due to the addition of aluminum and increased diffusivity due to the addition of a transition metal are both effective at the same time. This material would in principle work well for hydrogen storage but it is, unfortunately, unstable with respect to phase separation. A search was made for a ternary alloy of this type where both the alloy and the corresponding hydride are stable. Promising results were obtained by including Zn in the alloy.
Dias, Natália Martins; Gomes,Cristiano Mauro Assis; Reppold, Caroline Tozzi; Fioravanti-Bastos, Ana Carolina; Pires,Emmy Uehara; Carreiro, Luiz Renato Rodrigues; SEABRA,Alessandra Gotuzo
2015-01-01
Despite relative consensus on the existence of three basic executive functions (EF) (inhibition, working memory and cognitive flexibility) there is narrower knowledge on its organization and contribution to task solution. The study tested different theoretical models about the structure and composition of EF. The correlation matrix of Miyake et al. (2000), which evaluated university students in a set of 15 EF tasks, was adopted. Model 1 displays a general factor and specific components. In mo...
Theoretical studies on electron delocalisation in selenourea
Indian Academy of Sciences (India)
Rajnish Moudgil; Prasad V Bharatam; Ravneet Kaur; Damanjit Kaur
2002-06-01
Ab initio and density functional calculations have been performed on the different possible structures of selenourea (), urea () and thiourea () to understand the extent of delocalisation in selenourea in comparison to urea and thiourea. Selenourea (-1) with 2 symmetry has the minima on the potential energy surface at MP2(fu)/6-31+G* level. The C-N rotational barrier in selenourea is 8.69 kcal/mol, which is 0.29 and 0.11 kcal/mol more than that of urea and thiourea respectively at MP2(fu)/6-31+G* level. N-inversion barrier is 0.55 kcal/mol at MP2(fu)6-31+G* level. NBO analysis has been carried out to understand the nature of different interactions responsible for the electron delocalisation.
A Theoretical Study of Subsurface Drainage Model Simulation of ...
African Journals Online (AJOL)
A Theoretical Study of Subsurface Drainage Model Simulation of Drainage Flow and ... of subsurface drain spacing, evapotranspiration and irrigation water quality on ... The study was carried out on a conceptual uniform homogenous irrigated ...
Novel Pyranopyrazoles: Synthesis and Theoretical Studies
Directory of Open Access Journals (Sweden)
Abdul Amir H. Kadhum
2012-08-01
Full Text Available A series of pyranopyrazoles, namely, 7-(2-aminoethyl-3,4-dimethyl-1-phenyl-1H-pyrazolo[3,4-b]pyridin-6(7H-one (2, (Z-3,4-dimethyl-1-(4-((4-nitrobenzylideneaminophenylpyrano[2,3-c]pyrazol-6(1H-one (5, 1-(4-(3,4-dimethyl-6-oxopyrano[2,3-c]pyrazol-1(6H-ylphenyl-3-(naphthalen-1-ylurea (6, (Z-ethyl 4-((3,4-dimethyl-6-oxo-1,6-dihydropyrano[2,3-c]pyrazol-5-yldiazenylbenzoate (8 and 3,4-dimethyl-N-(naphthalen-1-yl-6-oxopyrano[2,3-c]pyrazole-1(6H-carboxamide (9 were synthesized and characterized by means of their UV-VIS, FT-IR, ^{1}H-NMR and ^{13}C-NMR spectral data. Density Functional Theory calculations of the synthesized pyranopyrazoles were performed using molecular structures with optimized geometries. Molecular orbital calculations have provided detail description of the orbitals, including spatial characteristics, nodal patterns, and the contributions of individual atoms.
Theoretical Studies of Long Lived Plasma Structures
Dvornikov, Maxim
2010-01-01
We construct the model of a long lived plasma structure based on spherically symmetric oscillations of electrons in plasma. Oscillations of electrons are studied in frames of both classical and quantum approaches. We obtain the density profile of electrons and the dispersion relations for these oscillations. The differences between classical and quantum approaches are discussed. Then we study the interaction between electrons participating in spherically symmetric oscillations. We find that this interaction can be attractive and electrons can form bound states. The applications of the obtained results to the theory of natural plasmoids are considered.
Leader genes in osteogenesis: a theoretical study.
Orlando, Bruno; Giacomelli, Luca; Ricci, Massimiliano; Barone, Antonio; Covani, Ugo
2013-01-01
Little is still known about the molecular mechanisms involved in the process of osteogenesis. In this paper, the leader genes approach, a new bioinformatics method which has already been experimentally validated, is adopted in order to identify the genes involved in human osteogenesis. Interactions among genes are then calculated and genes are ranked according to their relative importance in this process. In total, 167 genes were identified as being involved in osteogenesis. Genes were divided into 4 groups, according to their main function in the osteogenic processes: skeletal development; cell adhesion and proliferation; ossification; and calcium ion binding. Seven genes were consistently identified as leader genes (i.e. the genes with the greatest importance in osteogenesis), while 14 were found to have slightly less importance (class B genes). It was interesting to notice that the larger part of leader and class B genes belonged to the cell adhesion and proliferation or to the ossification sub-groups. This finding suggested that these two particular sub-processes could play a more important role in osteogenesis. Moreover, among the 7 leader genes, it is interesting to notice that RUNX2, BMP2, SPARC, PTH play a direct role in bone formation, while the 3 other leader genes (VEGF, IL6, FGF2) seem to be more connected with an angiogenetic process. Twenty-nine genes have no known interactions (orphan genes). From these results, it may be possible to plan an ad hoc experimentation, for instance by microarray analyses, focused on leader, class B and orphan genes, with the aim to shed new light on the molecular mechanisms underlying osteogenesis.
A Theoretical Study of Leading Edge Noise
2008-05-01
measurements of the noise radiated from a number of different airfoils made as -part of a companion study at Virginia lech . It was concluded that the...vectors in the direction normal to the local flow velocity and in the spanwise direction respectively. The transport equation for the vorticity is
Theoretical and Experimental Studies in Reactive Scattering.
1986-08-11
containing He and the neutral beam formed, cleansed of ions by appropriate electrostatic deflection plates, is reionized in a second charge exchange...H3 (having D3h symmetry) which could therefore support bound states. The technique of neutralization and reionization of H’ in order to study H 3 was...technique has been used again recently by Gaillard and co-workers 7 . By placing an electric field between the neutralization and reionization gas cells they
Experimental and theoretical study of Rayleigh-Lamb wave propagation
Rogers, Wayne P.; Datta, Subhendu K.; Ju, T. H.
1990-01-01
Many space structures, such as the Space Station Freedom, contain critical thin-walled components. The structural integrity of thin-walled plates and shells can be monitored effectively using acoustic emission and ultrasonic testing in the Rayleigh-Lamb wave frequency range. A new PVDF piezoelectric sensor has been developed that is well suited to remote, inservice nondestructive evaluation of space structures. In the present study the new sensor was used to investigate Rayleigh-Lamb wave propagation in a plate. The experimental apparatus consisted of a glass plate (2.3 m x 25.4 mm x 5.6 mm) with PVDF sensor (3 mm diam.) mounted at various positions along its length. A steel ball impact served as a simulated acoustic emission source, producing surface waves, shear waves and longitudinal waves with dominant frequencies between 1 kHz and 200 kHz. The experimental time domain wave-forms were compared with theoretical predictions of the wave propagation in the plate. The model uses an analytical solution for the Green's function and the measured response at a single position to predict response at any other position in the plate. Close agreement was found between the experimental and theoretical results.
Theoretical study of disorder induced magnetoresistance in graphene
Adam, Shaffique; Ping, Jinglei; Yudhistira, Indra; Ramakrishnan, Navneeth; Cho, Sungjae; Fuhrer, Michael S.
2014-03-01
In this work we predict theoretically that carrier density inhomogeneity provides a new mechanism for classical magnetoresistance. For concreteness, we study the case of graphene where density inhomogeneity and carrier scattering is dominated by charged impurities, although the mechanism itself is quite general and applies to other systems in which there are large spatial fluctuations of the carrier density. Calculations using an effective medium approximation show that low-field magnetoresistance becomes a universal function of the ratio between the average carrier density and the fluctuations of the carrier density, and scales as a power-law when this ratio is large. Our finding is in excellent agreement with recent experimental results. This work is supported by the Singapore National Research Foundation NRF-NRFF2012-01.
Theoretical Study on Reaction Mechanism of Aluminum-Water System
Institute of Scientific and Technical Information of China (English)
Yun-lan Sun; Yan Tian; Shu-fen Li
2008-01-01
A theoretical study on the reaction of aluminum with water in the gas phase was performed using the hybrid density functional B3LYP and QCISD(T) methods with the 6-311+G(d,p) and the 6-311++G(d,p) basis sets. The results show that there are three possible reaction pathways that involve four isomers, seven transition structures, and two possible products for the reaction of aluminum with water. The two most favorable reaction pathways were found, whose intermediates and products agreed quite well with experimental results. The enthalpy and Gibbs free energy change of the reaction between AI and H2O at 298 and 2000 K were calculated. Some results are also in good agreement with the previous calculations or experimental results.
Electrochemistry of chlorogenic acid: experimental and theoretical studies
Energy Technology Data Exchange (ETDEWEB)
Namazian, Mansoor [Department of Chemistry, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of)]. E-mail: namazian@yazduni.ac.ir; Zare, Hamid R. [Department of Chemistry, Yazd University, P.O. Box 89195-741, Yazd (Iran, Islamic Republic of)
2005-08-10
Cyclic voltammetry, chronoamperometry and rotating disk electrode voltammetry as well as quantum chemical methods, are used for electrochemical study of chlorogenic acid, as an important biological molecule. The standard formal potential, diffusion coefficient, and heterogeneous electron transfer rate constant of chlorogenic acid in aqueous solution are investigated. Acidic dissociation constant of chlorogenic acid is also obtained. Quantum mechanical calculations on oxidation of chlorogenic acid in aqueous solution, using density functional theory are presented. The change of Gibbs free energy and entropy of oxidation of chlorogenic acid are calculated using thermochemistry calculations. The calculations in aqueous solution are carried out with the use of polarizable continuum solvation method. Theoretical standard electrode potential of chlorogenic acid is achieved to be 0.580 V versus standard calomel electrode (SCE) which is in agreement with the experimental value of 0.617 V obtained experimentally in this work. The difference is consistent with the values we previously reported for other quinone derivatives.
Theoretical studies on Santilli's intermediate nuclear fusions without radiations
Cai, Wei
2012-09-01
Experiments of intermediate controlled nuclear fusion are strongly supported by theoretical study. First, current investigation based on quantum mechanics has proved that under super-strong magnetic field, which can be produced by a sudden large current of arc, the wave function of electron cloud changes from a spherical shape to a toroidal shape, which explores nuclear of atom. Second, hadronic mechanics shows that when a trigger, for example, a sudden change of arc, pushes two explored nucleus into a distance of 10-13 cm, a non-unitary, non-linear and nonpotential interaction, introduced by Santilli, leads two nucleus strongly attract each other, while the effective mass of nucleus being renormalized and becomes larger, which leads to a new view of structure of nucleus and results to new types of nuclear fusion.
Experimental and theoretical study of reflux condensation
Energy Technology Data Exchange (ETDEWEB)
Bakke, Knut
1997-12-31
This thesis studies the separation of gas mixtures in a reflux condenser. also called a dephlegmator. Reflux condensation is separation of a gas mixture, in reflux flow with condensing liquid, under continuous heat removal. A numerical model of a dephlegmator for binary mixtures was developed. The model may readily be extended to multi-component mixtures, as the solution method is based on a matrix solver. Separation of a binary mixture in a reflux condenser test rig is demonstrated. The test facility contains a single-tube test section that was designed and built as part of the project. Test mixtures of propane and n-butane were used, and a total of 15 experiments are reported. Limited degree of separation was achieved due to limited heat transfer area and narrow boiling point range of the test mixture. The numerical model reproduces the experimental data within reasonable accuracy. Deviation between calculated and measured properties is less than 6% of the measured temperature and less than 5% of the measured flow rate. The model is based on mechanistic models of physical processes and is not calibrated or tuned to fit the experimental data. The numerical model is applied to a number of separation processes. These case studies show that the required heat transfer area increases rapidly with increments in top product composition (light component). Flooding limits the amount of reflux liquid. The dephlegmator is suitable for separation of feed mixtures that are rich in light components. The gliding temperature in the dephlegmation process enables utilization of top product as refrigerant, with subsequent energy saving as a result. 61 refs., 50 figs., 34 tabs.
Theoretical study of cisplatin adsorption on silica
Energy Technology Data Exchange (ETDEWEB)
Simonetti, S., E-mail: ssimonet@uns.edu.ar [Departamento de Fisica and IFISUR, Universidad Nacional del Sur-CONICET, Av. Alem 1253, 8000 Bahia Blanca (Argentina); Departamentos de Ciencias Basicas e Ingenieria Mecanica, Universidad Tecnologica Nacional, 11 de Abril 461, 8000 Bahia Blanca (Argentina); Company, A. Diaz; Brizuela, G.; Juan, A. [Departamento de Fisica and IFISUR, Universidad Nacional del Sur-CONICET, Av. Alem 1253, 8000 Bahia Blanca (Argentina)
2011-11-15
The adsorption of cisplatin and its complexes, cis-[PtCl(NH{sub 3}){sub 2}]{sup +} and cis-[Pt(NH{sub 3}){sub 2}]{sup 2+}, on a SiO{sub 2}(1 1 1) hydrated surface has been studied by the Atom Superposition and Electron Delocalization method. The adiabatic energy curves for the adsorption of the drug and its products on the delivery system were considered. The electronic structure and bonding analysis were also performed. The molecule-surface interactions are formed at expenses of the OH surface bonds. The more important interactions are the Cl-H bond for cis-[PtCl{sub 2}(NH{sub 3}){sub 2}] and cis-[PtCl(NH{sub 3}){sub 2}]{sup +} adsorptions, and the Pt-O interaction for cis-[Pt(NH{sub 3}){sub 2}]{sup 2+} adsorption. The Cl p orbitals and Pt s, p y d orbitals of the molecule and its complexes, and the s H orbital and, the s and p orbitals of the O atoms of the hydrated surface are the main contribution to the surface bonds.
Theoretical and Experimental Studies in Accelerator Physics
Energy Technology Data Exchange (ETDEWEB)
Rosenzweig, James [Univ. of California, Los Angeles, CA (United States). Dept. of Physics and Astronomy
2017-03-08
. We note also that PBPL graduates remain as close elaborators for the program after leaving UCLA. The UCLA PBPL program is a foremost developer of on-campus facilities, such as the Neptune and Pegasus Laboratories, providing a uniquely strong environment for student-based research. In addition, the PBPL is a strong user of off-campus national lab facilities, such as SLAC FACET and NLCTA, and the BNL ATF. UCLA has also vigorously participated in the development of these facilities. The dual emphases on off- and on-campus opportunities permit the PBPL to address in an agile way a wide selection of cutting-edge research topics. The topics embraced by this proposal illustrate this program aspect well. These include: GV/m dielectric wakefield acceleration/coherent Cerenkov radiation experiments at FACET (E-201) and the ATF; synergistic laser-excited dielectric accelerator and light source development; plasma wakefield (PWFA) experiments on “Trojan horse” ionization injection (FACET E-210), quasi-nonlinear PWFA at BNL and the production at Neptune high transformer ratio plasma wakes; the inauguration of a new type of RF photoinjector termed “hybrid” at UCLA, and application to PWFA; space-charge dominated beam and cathode/near cathode physics; the study of advanced IFEL systems, for very high energy gain and utilization of novel OAM modes; the physcis of inverse Compton scattering (ICS), with applications to e+ production and γγ colliders; electron diffraction; and advanced beam diagnostics using coherent imaging techniques. These subjects are addressed under the leadership of PBPL director Prof. James Rosenzweig in Task A, and Prof. Pietro Musumeci in Task J, which was initiated following his OHEP Outstanding Junior Investigator award.
Theoretical Studies of Elementary Hydrocarbon Species and Their Reactions
Energy Technology Data Exchange (ETDEWEB)
Allen, Wesley D. [Univ. of Georgia, Athens, GA (United States). Dept. of Chemistry. Center for Computational Quantum Chemistry; Schaefer, III, Henry F. [Univ. of Georgia, Athens, GA (United States). Dept. of Chemistry. Center for Computational Quantum Chemistry
2015-11-14
This is the final report of the theoretical studies of elementary hydrocarbon species and their reactions. Part A has a bibliography of publications supported by DOE from 2010 to 2016 and Part B goes into recent research highlights.
EXPERIMENTAL AND THEORETICAL NMR STUDY OF 4-(1 ...
African Journals Online (AJOL)
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3 Department of Physics, Arts and Science Faculty, Dumlupınar University, Kütahya, Turkey. 4 Department ... been studied experimentally and theoretically using nuclear magnetic resonance (NMR) spectroscopy. 1H, 13C, ... INTRODUCTION.
Stellar Mass Function of Lyman Break Galaxies: Theoretical Perspective
Institute of Scientific and Technical Information of China (English)
LIU Xiao-Liang; HUANG Yong-Qing; LIU Nian-Hua; LAI Zhen-Quan; SHU Cheng-Gang
2006-01-01
@@ Adopting the observational distributions of star formation rates and half-light radii of Lyman break galaxies (LBGs) in the rest frame UV, we investigate empirically the predicted stellar mass function for LBGs.
Theoretical study of the adsorption of benzene on coinage metals
Directory of Open Access Journals (Sweden)
Werner Reckien
2014-08-01
Full Text Available The adsorption of benzene on the M(111, M(100 and M(110 surfaces of the coinage metals copper (M = Cu, silver (M = Ag and gold (M = Au is studied on the basis of density functional theory (DFT calculations with an empirical dispersion correction (D3. Variants of the Perdew–Burke–Ernzerhof functionals (PBE, RPBE and RevPBE in combination with different versions of the dispersion correction (D3 and D3(BJ are compared. PBE-D3, PBE-D3(BJ and RPBE-D3 give similar results which exhibit a good agreement with experimental data. RevPBE-D3 and RevPBE-D3(BJ tend to overestimate adsorption energies. The inclusion of three-center terms (PBE-D3(ABC leads to a slightly better agreement with the experiment in most cases. Vertical adsorbate–substrate distances are calculated and compared to previous theoretical results. The observed trends for the surfaces and metals are consistent with the calculated adsorption energies.
An information theoretic approach to the functional classification of neurons
Schneidman, E; Berry, M J; Schneidman, Elad; Bialek, William; Berry, Michael J.
2002-01-01
A population of neurons typically exhibits a broad diversity of responses to sensory inputs. The intuitive notion of functional classification is that cells can be clustered so that most of the diversity is captured in the identity of the clusters rather than by individuals within clusters. We show how this intuition can be made precise using information theory, without any need to introduce a metric on the space of stimuli or responses. Applied to the retinal ganglion cells of the salamander, this approach recovers classical results, but also provides clear evidence for subclasses beyond those identified previously. Further, we find that each of the ganglion cells is functionally unique, and that even within the same subclass only a few spikes are needed to reliably distinguish between cells.
The strange history of B functions or how theoretical chemists and mathematicians do (not) interact
Weniger, Ernst Joachim
2008-01-01
$B$ functions are a class of relatively complicated exponentially decaying basis functions. Since the molecular multicenter integrals of the much simpler Slater-type functions are notoriously difficult, it is not at all obvious why $B$ functions should offer any advantages. However, $B$ functions have Fourier transforms of exceptional simplicity, which greatly simplifies many of their molecular multicenter integrals. This article discusses the historical development of $B$ functions from the perspective of the interaction between mathematics and theoretical chemistry, which traditionally has not been very good. Nevertheless, future progress in theoretical chemistry depends very much on a fertile interaction with neighboring disciplines.
Experimental and theoretical study on hollow-cone spray
Chang, Keh-Chin; Wang, Muh-Rong; Wu, Wen-Jing; Hong, Chia-Hong
1993-02-01
A theoretical and experimental investigation has been conducted to study the two-phase turbulent structure in an isothermal hollow-cone spray. Mean and fluctuating velocity components, drop number density, as well as drop-size distribution were measured with a nonintrusive diagnostic tool, a two-component phase Doppler particle analyzer. Complete initial conditions required for theoretical calculations were also provided with measurements. Theoretical calculations were made with an Eulerian-Lagrangian formulism. Turbulent dispersion effects were numerically simulated using a Monte Carlo method. Turbulence modulation effects were also taken into account in the modeling. The well-defined experimental data were used to assess the accuracy of the resultant Eulerian-Lagrangian model. Comparisons showed that the theoretical predictions, based upon the Eulerian-Lagrangian model, yielded reasonable agreement with the experimental data. The improvements made by inclusion of the selected turbulence modulation model were insignificant in this work.
Chronic job burnout and daily functioning: A theoretical analysis
Directory of Open Access Journals (Sweden)
Arnold B. Bakker
2014-12-01
Full Text Available In this article, we discuss the individual employee's role in the development of his/her job burnout. We review the antecedents and consequences of burnout, and propose a model with chronic burnout as a moderator of daily functioning in the workplace. Specifically, we argue that chronic burnout strengthens the loss cycle of daily job demands, daily exhaustion, and daily self-undermining. Additionally, we argue that chronic burnout weakens the gain cycle of daily job resources, daily work engagement, and daily job crafting. We conclude that employees with high levels of burnout need help in structurally changing their working conditions and health status.
Ohsaku, T; Yamaki, D; Yamaguchi, K
2002-01-01
For studying the group theoretical classification of the solutions of the density functional theory in relativistic framework, we propose quantum electrodynamical density-matrix functional theory (QED-DMFT). QED-DMFT gives the energy as a functional of a local one-body $4\\times4$ matrix $Q(x)\\equiv -$, where $\\psi$ and $\\bar{\\psi}$ are 4-component Dirac field and its Dirac conjugate, respectively. We examine some characters of QED-DMFT. After these preparations, by using Q(x), we classify the solutions of QED-DMFT under O(3) rotation, time reversal and spatial inversion. The behavior of Q(x) under nonrelativistic and ultrarelativistic limits are also presented. Finally, we give plans for several extensions and applications of QED-DMFT.
Institute of Scientific and Technical Information of China (English)
LIU Jun-Bo; SUN Jia-Ni; TANG Shan-Shan; CHEN Kai-Yin; JIN Rui-Fa
2012-01-01
As a widely used herbicide, the threat of atrazine to both environment and health of people has become the focus. Therefore, the research and analysis of atrazine are getting more important. In this work, the MIT was used to detect atrazine theoretically. Atrazine was taken as a template molecule. MAA, MMA and TFMAA were taken as the functional monomers, respectively. The geometry optimization, the nature of hydrogen bonds, the NBO charge, and the binding energies of the imprinted molecule with the functional monomers were investigated at the B3LYP/6-31g(d,p) level. Results indicated that atrazine had the strongest interaction with TFMAA. When the ratio of atrazine and TFMAA was 1:6, the amount of H-bond formed from atrazine and TFMAA was the largest. Moreover, TFMAA owned the largest binding energy with atrazine while MMA owned the smallest. The study is helpful to interpret experiment phenomena of molecular imprinting and select better functional monomers.
Theoretical Study on the Mechanism of Sonogashira Coupling Reaction
Institute of Scientific and Technical Information of China (English)
CHEN Li-Ping; HONG San-Guo; HOU Hao-Qing
2008-01-01
The mechanism of palladium-catalyzed Sonogashira cross-coupling reaction has been studied theoretically by DFT (density functional theory) calculations. The model system studied consists of Pd(PH3)2 as the starting catalyst complex, phenyl bromide as the substrate and acetylene as the terminal alkyne, without regarding to the co-catalyst and base. Mechanistically and energetically plausible catalytic cycles for the cross-coupling have been identified. The DFT analysis shows that the catalytic cycle occurs in three stages: oxidative addition of phenyl bromide to the palladium center, alkynylation of palladium(II) intermediate, and reductive elimination to phenylacetylene. In the oxidative addition, the neutral and anionic pathways have been investigated, which could both give rise to cis-configured palladium(II) diphosphine intermediate. Starting from the palladium(II) diphosphine intermediate, the only identifiable pathway in alkynylation involves the dissociation of Br group and the formation of square-planar palladium(II) intermediate, in which the phenyl and alkynyl groups are oriented cis to each other. Due to the close proximity of phenyl and alkynyl groups, the reductive elimination of phenylacetylene proceeds smoothly.
Piezoelectricity in quasicrystals: A group-theoretical study
Indian Academy of Sciences (India)
K Rama Rao; P Hemagiri Rao; B S K Chaitanya
2007-03-01
Group-theoretical methods have been accepted as exact and reliable tools in studying the physical properties of crystals and quasicrystalline materials. By group representation theory, the maximum number of non-vanishing and independent second- order piezoelectric coefficients required by the seven pentagonal and two icosahedral point groups - that describe the quasicrystal symmetry groups in two and three dimensions - is determined. The schemes of non-vanishing and independent second-order piezoelectric tensor components needed by the nine point groups with five-fold rotations are identified and tabulated employing a compact notation. The results of this group-theoretical study are briefly discussed.
Diffusion in liquids a theoretical and experimental study
Tyrrell, H J V
1984-01-01
Diffusion in Liquids: A Theoretical and Experimental Study aims to discuss the principles, applications, and advances in the field of diffusion, thermal diffusion, and thermal conduction in liquid systems. The book covers topics such as the principles of non-equilibrium thermodynamics; diffusion in binary and multicompetent systems; and experimental methods of studying diffusion processes in liquids. Also covered in the book are topics such as the theoretical interpretations of diffusion coefficients; hydrodynamic and kinetic theories; and diffusion in electrolyte systems. The text is recommen
Theoretical and Methodological Perspectives on Designing Video Studies of Interaction
Directory of Open Access Journals (Sweden)
Anna-Lena Rostvall
2005-12-01
Full Text Available In this article the authors discuss the theoretical basis for the methodological decisions made during the course of a Swedish research project on interaction and learning. The purpose is to discuss how different theories are applied at separate levels of the study. The study is structured on three levels, with separate sets of research questions and theoretical concepts. The levels reflect a close-up description, a systematic analysis, and an interpretation of how teachers and students act and interact. The data consist of 12 hours of video-recorded and transcribed music lessons from high school and college. Through a multidisciplinary theoretical framework, the general understanding of teaching and learning in terms of interaction can be widened. The authors also present a software tool developed to facilitate the processes of transcription and analysis of the video data.
THE THEORETICAL STUDY OF ADSORPTION OF METAL IONS ON CHITOSAN
Institute of Scientific and Technical Information of China (English)
无
2005-01-01
The interactions between metal ions such as Zn2+, Pb2+, Mn2+, Hg2+, Cd2+, Ni2+ and chitosan have been investigated using the model cluster model method and density functional method. Full optimization and frequency analysis of all cluster models have been performed employing B3LYP hybrid method at 3-21G basis set level except metal ions which were invoked to use effective core potential (ECP) method. The energy changes, and the main structural parameters have been obtained during the theoretical study of the adsorption of metal ions on the chitosan. The calculations showed that the coordination modes of metal ions with chitosan models were different, the geometries of Mn2+, Zn2+, Cd2+, Hg2+, Pb2+ ions coordinated with two nitrogen atoms and two oxygen atoms were distorted tetrahedral, while the square planar structure of Ni2+ coordinated two nitrogen atoms and two oxygen atoms was observed. The heat of reaction between six metal ions and chitosan models showed the order: Mn2+ ＞Ni2+ ＞Zn2+ ＞Pb2+ ＞Hg2+ ＞Cd2+, this suggested that the coordination strength of Mn2+ ＞Ni2+ ＞Zn2+ ＞Pb2+ ＞Hg2+ ＞Cd2+.
Properties of Some Kind of Number Theoretical Function(Ⅱ)%一类数论函数的性质(Ⅱ)
Institute of Scientific and Technical Information of China (English)
李怡君; 刘华柯
2007-01-01
For any given positive integer n ≥ 1, the Euler function (ψ)(n) is defined to be the number of positive integers not exceeding n, which is relatively prime to n. ω(n) is defined to be the number of different prime divisors of n. In order to know the solvability of the function of (ψ)((ψ)((ψ)(n))) = 2ω(n), properties of the number theoretical function (ψ)((ψ)(n)) is studied in the paper.
Theoretical model for mesoscopic-level scale-free self-organization of functional brain networks.
Piersa, Jaroslaw; Piekniewski, Filip; Schreiber, Tomasz
2010-11-01
In this paper, we provide theoretical and numerical analysis of a geometric activity flow network model which is aimed at explaining mathematically the scale-free functional graph self-organization phenomena emerging in complex nervous systems at a mesoscale level. In our model, each unit corresponds to a large number of neurons and may be roughly seen as abstracting the functional behavior exhibited by a single voxel under functional magnetic resonance imaging (fMRI). In the course of the dynamics, the units exchange portions of formal charge, which correspond to waves of activity in the underlying microscale neuronal circuit. The geometric model abstracts away the neuronal complexity and is mathematically tractable, which allows us to establish explicit results on its ground states and the resulting charge transfer graph modeling functional graph of the network. We show that, for a wide choice of parameters and geometrical setups, our model yields a scale-free functional connectivity with the exponent approaching 2, which is in agreement with previous empirical studies based on fMRI. The level of universality of the presented theory allows us to claim that the model does shed light on mesoscale functional self-organization phenomena of the nervous system, even without resorting to closer details of brain connectivity geometry which often remain unknown. The material presented here significantly extends our previous work where a simplified mean-field model in a similar spirit was constructed, ignoring the underlying network geometry.
A theoretical model for smoking prevention studies in preteen children.
McGahee, T W; Kemp, V; Tingen, M
2000-01-01
The age of the onset of smoking is on a continual decline, with the prime age of tobacco use initiation being 12-14 years. A weakness of the limited research conducted on smoking prevention programs designed for preteen children (ages 10-12) is a well-defined theoretical basis. A theoretical perspective is needed in order to make a meaningful transition from empirical analysis to application of knowledge. Bandura's Social Cognitive Theory (1977, 1986), the Theory of Reasoned Action (Ajzen & Fishbein, 1980), and other literature linking various concepts to smoking behaviors in preteens were used to develop a model that may be useful for smoking prevention studies in preteen children.
Theoretical and Experimental Study of Time Reversal in Cubic Crystals
Institute of Scientific and Technical Information of China (English)
陆铭慧; 张碧星; 汪承灏
2004-01-01
The self-adaptive focusing of the time reversal in anisotropic media is studied theoretically and experimentally. It is conducted for the compressional wave field in the cubic crystal silicon. The experimental result is in agreement with our theoretical analysis. The focusing gain and the displacement distributions of the time reversal field are analysed in detail. It is shown that the waves from different elements of the transducer array arrive at the original place of the source simultaneously after the time reversal operation. The waveform distortions caused by the velocity anisotropy can automatically be compensated for after the time reversal processing.
Theoretical studies on kinetics of singlet oxygen in nonthermal plasma
Frolov, Mikhail P.; Ionin, Andrei A.; Kotkov, Andrei A.; Kochetov, Igor V.; Napartovich, Anatolii P.; Podmarkov, Yurii P.; Seleznev, Leonid V.; Sinitsyn, Dmitrii V.; Vagin, Nikolai P.; Yuryshev, Nikolay N.
2004-09-01
An idea to replace singlet delta oxygen (SDO) generator working with wet chemistry by electric discharge generator has got much attention last years. Different kinds of discharge were examined for this purpose, but without a great success. The existing theoretical models are not validated by well-characterized experimental data. To describe complicated kinetics in gas discharge with oxygen one needs to know in detail processes involving numerous electronic excited oxygen molecules and atoms. To gain new knowledge about these processes experimental studies were made on electric discharge properties in gas mixture flow with independent control of inlet SDO concentration. The theoretical model extended to include minor additives like oxygen atoms, water molecules, ozone was developed. Comparison with careful experimental measurements of electric characteristics along with gas composition allows us to verify the model and make theoretical predictions more reliable. Results of numerical simulations using this model for an electron-beam sustained discharge are reported and compared with the experimental data.
DERIVATIVE OF SET MEASURE FUNCTIONS AND ITS APPLICATION (THEORETICAL BASES OF INVESTMENT OBJECTIVES
Directory of Open Access Journals (Sweden)
A. A. Bosov
2014-04-01
Full Text Available Purpose. It is necessary to develop the theoretical fundamentals for solving the investment objectives presented in the form of set function as vector optimization tasks or tasks of constrained extremum. Methodology. Set functions and their derivatives of measure are used as research of investment objectives. Necessary condition of set function minimum is proved. In the tasks for constrained extremum the method of Lagrange is used. It is shown that this method can also be used for the set function. It is used the measure for proof, which generalizes the Lebesgue measure, and the concept of set sequence limit is introduced. It is noted that the introduced limit over a measure coincides with the classical Borel limit and can be used in order to prove the existence of derivative from set function over a measure on convergent of sets sequence. Findings. An algorithm of solving the investment objective for constrained extremum in relation to investment objectives was offered. Originality. Scientific novelty lies in the fact that in multivariate objects for constrained extremum one can refuse from immediate enumeration. One can use the proposed algorithm of constructing (selection of options that allow building a convex linear envelope of Pareto solutions. This envelope will let the person who makes a decision (DM, select those options that are "better" from a position of DM, and consider some of the criteria, the formalization of which are difficult or can not be described in mathematical terms. Practical value. Results of the study provide the necessary theoretical substantiation of decision-making in investment objectives, when there is a significant number of an investment objects and immediate enumeration of options is very difficult on time costs even for modern computing techniques.
The chirally rotated Schrödinger functional: theoretical expectations and perturbative tests
Energy Technology Data Exchange (ETDEWEB)
Brida, Mattia Dalla [NIC, DESY,Platanenallee 6, 15738 Zeuthen (Germany); Sint, Stefan [School of Mathematics, Trinity College Dublin,Dublin 2 (Ireland); Vilaseca, Pol [Istituto Nazionale di Fisica Nucleare, Sezione di Roma,P.le A. Moro 2, I-00185, Roma (Italy)
2016-08-17
The chirally rotated Schrödinger functional (χSF) with massless Wilson-type fermions provides an alternative lattice regularization of the Schrödinger functional (SF), with different lattice symmetries and a common continuum limit expected from universality. The explicit breaking of flavour and parity symmetries needs to be repaired by tuning the bare fermion mass and the coefficient of a dimension 3 boundary counterterm. Once this is achieved one expects the mechanism of automatic O(a) improvement to be operational in the χSF, in contrast to the standard formulation of the SF. This is expected to significantly improve the attainable precision for step-scaling functions of some composite operators. Furthermore, the χSF offers new strategies to determine finite renormalization constants which are traditionally obtained from chiral Ward identities. In this paper we consider a complete set of fermion bilinear operators, define corresponding correlation functions and explain the relation to their standard SF counterparts. We discuss renormalization and O(a) improvement and then use this set-up to formulate the theoretical expectations which follow from universality. Expanding the correlation functions to one-loop order of perturbation theory we then perform a number of non-trivial checks. In the process we obtain the action counterterm coefficients to one-loop order and reproduce some known perturbative results for renormalization constants of fermion bilinears. By confirming the theoretical expectations, this perturbative study lends further support to the soundness of the χSF framework and prepares the ground for non-perturbative applications.
The chirally rotated Schrödinger functional: theoretical expectations and perturbative tests
Brida, Mattia Dalla; Sint, Stefan; Vilaseca, Pol
2016-08-01
The chirally rotated Schrödinger functional (χSF) with massless Wilson-type fermions provides an alternative lattice regularization of the Schrödinger functional (SF), with different lattice symmetries and a common continuum limit expected from universality. The explicit breaking of flavour and parity symmetries needs to be repaired by tuning the bare fermion mass and the coefficient of a dimension 3 boundary counterterm. Once this is achieved one expects the mechanism of automatic O( a) improvement to be operational in the χSF, in contrast to the standard formulation of the SF. This is expected to significantly improve the attainable precision for step-scaling functions of some composite operators. Furthermore, the χSF offers new strategies to determine finite renormalization constants which are traditionally obtained from chiral Ward identities. In this paper we consider a complete set of fermion bilinear operators, define corresponding correlation functions and explain the relation to their standard SF counterparts. We discuss renormalization and O( a) improvement and then use this set-up to formulate the theoretical expectations which follow from universality. Expanding the correlation functions to one-loop order of perturbation theory we then perform a number of non-trivial checks. In the process we obtain the action counterterm coefficients to one-loop order and reproduce some known perturbative results for renormalization constants of fermion bilinears. By confirming the theoretical expectations, this perturbative study lends further support to the soundness of the χSF framework and prepares the ground for non-perturbative applications.
Taghian, Toloo; Sheikh, Abdul; Narmoneva, Daria; Kogan, Andrei
2015-03-01
Application of external electric field (EF) as a non-pharmacological, non-invasive tool to control cell function is of great therapeutic interest. We developed a theoretical-experimental approach to investigate the biophysical mechanisms of EF interaction with cells in electrode-free physiologically-relevant configuration. Our numerical results demonstrated that EF frequency is the major parameter to control cell response to EF. Non-oscillating or low-frequency EF leads to charge accumulation on the cell surface membrane that may mediate membrane initiated cell responses. In contrast, high-frequency EF penetrates the cell membrane and reaches cell cytoplasm, where it may directly activate intracellular responses. The theoretical predictions were confirmed in our experimental studies of the effects of applied EF on vascular cell function. Results show that non-oscillating EF increases vascular endothelial growth factor (VEGF) expression while field polarity controls cell adhesion rate. High-frequency, but not low frequency, EF provides differential regulation of cytoplasmic focal adhesion kinase and VEGF expression depending on the substrate, with increased expression in cells cultured on RGD-rich synthetic hydrogels, and decreased expression for matrigel culture. The authors acknowledge the financial support from the NSF (DMR-1206784 & DMR-0804199 to AK); the NIH (1R21 DK078814-01A1 to DN) and the University of Cincinnati (Interdisciplinary Faculty Research Support Grant to DN and AK).
The Impact of Theoretical Uncertainties in the Halo Mass Function and Halo
Energy Technology Data Exchange (ETDEWEB)
Wu, Hao-Yi; Zentner, Andrew R.; Wechsler, Risa H.; /KIPAC, Menlo Park /SLAC /Pittsburgh U. /KIPAC, Menlo Park /SLAC
2010-06-04
We study the impact of theoretical uncertainty in the dark matter halo mass function and halo bias on dark energy constraints from imminent galaxy cluster surveys. We find that for an optical cluster survey like the Dark Energy Survey, the accuracy required on the predicted halo mass function to make it an insignificant source of error on dark energy parameters is {approx}1%. The analogous requirement on the predicted halo bias is less stringent ({approx}5%), particularly if the observable-mass distribution can be well constrained by other means. These requirements depend upon survey area but are relatively insensitive to survey depth. The most stringent requirements are likely to come from a survey over a significant fraction of the sky that aims to observe clusters down to relatively low mass, M{sub th}{approx} 10{sup 13.7} h{sup -1} M{sub sun}; for such a survey, the mass function and halo bias must be predicted to accuracies of {approx}0.5% and {approx}1%, respectively. These accuracies represent a limit on the practical need to calibrate ever more accurate halo mass and bias functions. We find that improving predictions for the mass function in the low-redshift and low-mass regimes is the most effective way to improve dark energy constraints.
Theoretical foundations of functional data analysis, with an introduction to linear operators
Hsing, Tailen
2015-01-01
Theoretical Foundations of Functional Data Analysis, with an Introduction to Linear Operators provides a uniquely broad compendium of the key mathematical concepts and results that are relevant for the theoretical development of functional data analysis (FDA).The self-contained treatment of selected topics of functional analysis and operator theory includes reproducing kernel Hilbert spaces, singular value decomposition of compact operators on Hilbert spaces and perturbation theory for both self-adjoint and non self-adjoint operators. The probabilistic foundation for FDA is described from the
Dimerization of Indanedioneketene to Spiro-oextanone: A Theoretical Study
Energy Technology Data Exchange (ETDEWEB)
Bakalbassis, Evangelos G; Malamidou-Xenikaki, Elizabeth; Spyroudis, Spyros; Xantheas, Sotiris S
2010-08-20
Indanedioneketene, a compound resulting from the thermal degradation of the phenyliodonium ylide of lawsone, dimerises quantitatively to a spiro-oxetanone derivative, a key compound for further transformations. A theoretical DFT study of this unusual for α-oxoketenes [2+2] cyclization reaction both in the gas phase and in dichloromethane solution, provides support for a) a single-step, transitionstate (involving a four-membered cyclic ring) charge controlled, concerted mechanism, and b) a [4+2] cyclization reaction, not observed but studied theoretically in this study. A parallel study of an open chain α,α'-dioxoketene dimerization explains the difference in the stability and reactivity observed experimentally between the cyclic and open chain products.
Energy Technology Data Exchange (ETDEWEB)
Bretagne, J. (Paris-11 Univ., 91 - Orsay (France)); Graham, W.G. (Queen' s Univ., Belfast, Northern Ireland (UK). Dept. of Physics); Hopkins, M.B. (Dublin City Univ. (Ireland). Dept. of Physics)
1991-05-14
Experimental and theoretical electron energy distribution functions (EEDFS) measured in and calculated for the driver of a multicusp ion source operating in hydrogen are compared. The results show that atomic physics based theoretical models can accurately predict the EEDF in such discharges if some appropriate experimentally determined quantities are used as input parameters. The magnitude and shape of the EEDF is found to be particularly sensitive to the effective surface area to volume ratio for electrons. (author).
Theoretical study of the dipole moment of oxygen monofluoride (OF)
Langhoff, S. R.; Bauschlicher, C. W., Jr.; Partridge, H.
1983-01-01
The ground-state potential curve and dipole-moment function of OF are calculated theoretically using the complete active-space self-consistent-field levels, externally contracted configuration-interaction levels, or multireference (singles plus doubles) configuration-interaction levels. Both an extended Gaussian basis set and a double-zeta-plus-polarization basis set were applied. The results are presented in extensive tables and graphs. Best results are achieved using a large Gaussian basis set and taking the valence-correlation energy into account. It is suggested that OF may best be detected by its laser-magnetic-resonance spectrum in the IR.
Theoretical and material studies on thin-film electroluminescent devices
Summers, C. J.; Goldman, J. A.; Brennan, K.
1988-01-01
During this report period work was performed on the modeling of High Field Electronic Transport in Bulk ZnS and ZnSe, and also on the surface cleaning of Si for MBE growth. Some MBE growth runs have also been performed in the Varian GEN II System. A brief outline of the experimental work is given. A complete summary will be done at the end of the next reporting period at the completion of the investigation. The theoretical studies are included.
Experimental and theoretical study on the electrospinning nanoporous fibers process
Energy Technology Data Exchange (ETDEWEB)
Zhao, Jianghui; Si, Na [National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University, Suzhou (China); Xu, Lan, E-mail: lanxu@suda.edu.cn [National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University, Suzhou (China); Nantong Textile Institute of Soochow University, Nantong (China); Tang, Xiaopeng; Song, Yanhua; Sun, Zhaoyang [National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University, Suzhou (China)
2016-02-15
Porous materials can be prepared by sol–gel method, hydrothermal synthesis method, electrospinning and other methods. In this paper, electrospun porous nanofibers were prepared by adjusting electrospinning parameters. And the properties of obtained porous nanofiber mats were investigated. Theoretical analysis and experiment research were carried out to research mechanical mechanism of electrospun porous nanofibers, and could be used to optimize and control the porous structure. The theoretical analysis results were further verified according to the experimental data. In addition, Bernoulli equation was used to study the electrospinning “splaying” process. We found the ratio of pore width to pore length was varied along with the variation of the internal pressure of the jet, and the internal pressure of the jet increases with the velocity of the charged jet decreases. - Highlights: • Mechanical mechanism of electrospun porous nanofibers process was studied. • A simplifying gas–liquid two-phase flow model was established. • Bernoulli equation was used to study the electrospinning “splaying” process. • The theoretical results were in good agreement with the experimental data. • The electrospinning parameters affected the surface morphology of charged jet.
Sociomateriality: a theoretical framework for studying distributed medical education.
MacLeod, Anna; Kits, Olga; Whelan, Emma; Fournier, Cathy; Wilson, Keith; Power, Gregory; Mann, Karen; Tummons, Jonathan; Brown, Peggy Alexiadis
2015-11-01
Distributed medical education (DME) is a type of distance learning in which students participate in medical education from diverse geographic locations using Web conferencing, videoconferencing, e-learning, and similar tools. DME is becoming increasingly widespread in North America and around the world.Although relatively new to medical education, distance learning has a long history in the broader field of education and a related body of literature that speaks to the importance of engaging in rigorous and theoretically informed studies of distance learning. The existing DME literature is helpful, but it has been largely descriptive and lacks a critical "lens"-that is, a theoretical perspective from which to rigorously conceptualize and interrogate DME's social (relationships, people) and material (technologies, tools) aspects.The authors describe DME and theories about distance learning and show that such theories focus on social, pedagogical, and cognitive considerations without adequately taking into account material factors. They address this gap by proposing sociomateriality as a theoretical framework allowing researchers and educators to study DME and (1) understand and consider previously obscured actors, infrastructure, and other factors that, on the surface, seem unrelated and even unimportant; (2) see clearly how the social and material components of learning are intertwined in fluid, messy, and often uncertain ways; and (3) perhaps think differently, even in ways that disrupt traditional approaches, as they explore DME. The authors conclude that DME brings with it substantial investments of social and material resources, and therefore needs careful study, using approaches that embrace its complexity.
Lee, Jungsoo; Lee, Minji; Kim, Dae-Shik; Kim, Yun-Hee
2015-01-01
This study investigated the changes in the network topological configuration of the ipsilesional and contralesional hemispheres after a stroke and the indicators for the prediction of motor recovery using a graph theoretical approach in networks obtained from functional magnetic resonance imaging (fMRI). A longitudinal observational experiments (2 weeks and 1, 3, and 6 months after onset) were conducted on 12 patients after a stroke. We investigated the network reorganization during recovery in the ipsilesional and contralesional hemispheres by examining changes of graph indices related to network randomization. We predicted the recovery of motor function by examining the relationship between specific network measures and improved motor function scores. The ipsilesional hemispheric network showed active reorganization during recovery after a stroke. The randomness of the network significantly increased for 3 months post-stroke. We described an indicator for the prediction of the recovery of motor function from graph indices: the characteristic path length. As the path length of the ipsilesional network was lower immediately after onset, the better recovery could be expected after 3 months. This approach were helpful for understanding dynamic reorganizations of both hemispheric networks after a stroke and finding the implication for recovery.
Theoretical and Experimental Study of Plasmonic Polymer Solar Cells
DEFF Research Database (Denmark)
Mirsafaei, Mina; Adam, Jost; Madsen, Morten
The organic bulk hetero-junction solar cell has remarkable advantages such as low cost, mechanical flexibility and simple process techniques. Recently, low-band gap photoactive materials have obtained a significant attention due to their potential to absorb a wider range of the solar spectrum...... other approaches, be achieved by using nano- or micro-structures that trap light at specific wavelengths [2], or by using the localized surface plasmon resonance effect of metal nanoparticles in the devices. In this work, we theoretically studied planar polymer solar cell based on finite-difference time......-domain approach. Also, we have optimized reference polymer solar cells with PTB7:PC70BM as active layer, using two different electron transport layers. The aim is to integrate Gold nanoparticles in the reference devices, and support the integration theoretically....
Statistical and theoretical studies of flares from Sagittarius A*
Li, Ya-Ping; Yuan, Qiang; Wang, Q. Daniel; Chen, P. F.; Neilsen, Joseph; Fang, Taotao; Zhang, Shuo; Dexter, Jason
2017-01-01
Multi-wavelength flares have routinely been observed from the supermassive black hole, Sagittarius A* (Sgr A*), at our Galactic center. The nature of these flares remains largely unclear, despite many theoretical models. We study the statistical properties of the Sgr A* X-ray flares and find that they are consistent with the theoretical prediction of the self-organized criticality system with the spatial dimension S = 3. We suggest that the X-ray flares represent plasmoid ejections driven by magnetic reconnection (similar to solar flares) in the accretion flow onto the black hole. Motivated by the statistical results, we further develop a time-dependent magnetohydrodynamic (MHD) model for the multi-band flares from Sgr A* by analogy with models of solar flares/coronal mass ejections (CMEs). We calculate the X-ray, infrared flare light curves, and the spectra, and find that our model can explain the main features of the flares.
THEORETICAL AND EXPERIMENTAL STUDY OF STRUCTURES SUBJECTED TO EARTHQUAKES
Energy Technology Data Exchange (ETDEWEB)
Soubirou, A.
1967-12-31
The object of the study was the investigation of the behaviour of structures subject to earthquakes. After .describing and analysing seismic movements, useful concepts for earthquake-proofing structures are lintroduced. Then, the dynamic behaviour of systems with n degrees of freedom was studied in order to evolve the theoretical computation of seismic behaviour, a typical application being reticulated structures. The next stage was showing the computational procedure for seismic spectra and the natural frequencies of buildings, an attempt being made to define earthquake-proofing criteria for a special type of reinforced-concrete construction. . The last matter dealt with is elastoplastic behaviour of structures, a study of increasingly growing importance.
Barnes-Holmes, Dermot; Hussey, Ian
2016-02-01
The functional-cognitive meta-theoretical framework has been offered as a conceptual basis for facilitating greater communication and cooperation between the functional/behavioural and cognitive traditions within psychology, thus leading to benefits for both scientific communities. The current article is written from the perspective of two functional researchers, who are also proponents of the functional-cognitive framework, and attended the "Building Bridges between the Functional and Cognitive Traditions" meeting at Ghent University in the summer of 2014. The article commences with a brief summary of the functional approach to theory, followed by our reflections upon the functional-cognitive framework in light of that meeting. In doing so, we offer three ways in which the framework could be clarified: (a) effective communication between the two traditions is likely to be found at the level of behavioural observations rather than effects or theory, (b) not all behavioural observations will be deemed to be of mutual interest to both traditions, and (c) observations of mutual interest will be those that serve to elaborate and extend existing theorising in the functional and/or cognitive traditions. The article concludes with a summary of what we perceive to be the strengths and weaknesses of the framework, and a suggestion that there is a need to determine if the framework is meta-theoretical or is in fact a third theoretical approach to doing psychological science.
Energy Technology Data Exchange (ETDEWEB)
Lind, M. [Oersted - DTU, Kgs. Lyngby (Denmark)
2005-10-01
Multilevel Flow Modeling (MFM) has proven to be an effective modeling tool for reasoning about plant failure and control strategies and is currently exploited for operator support in diagnosis and on-line alarm analysis. Previous MFM research was focussed on representing goals and functions of process plants which generate, transform and distribute mass and energy. However, only a limited consideration has been given to the problems of modeling the control systems. Control functions are indispensable for operating any industrial plant. But modeling of control system functions has proven to be a more challenging problem than modeling functions of energy and mass processes. The problems were discussed by Lind and tentative solutions has been proposed but have not been investigated in depth until recently, partly due to the lack of an appropriate theoretical foundation. The purposes of the present report are to show that such a theoretical foundation for modeling goals and functions of control systems can be built from concepts and theories of action developed by Von Wright and to show how the theoretical foundation can be used to extend MFM with concepts for modeling control systems. The theoretical foundations has been presented in detail elsewhere by the present author without the particular focus on modeling control actions and MFM adopted here. (au)
Theoretical study for solar air pretreatment collector/regenerator
Energy Technology Data Exchange (ETDEWEB)
Peng Donggen; Zhang Xiaosong; Yin Yonggao [School of Energy and Environment, Southeast Univ., Nanjing (China)
2008-07-01
A new liquid regeneration equipment - solar air pretreatment collector/regenerator for liquid desiccant cooling system is put forward in this paper, which is preferable to solution regeneration in hot and moist climate in South China. The equipment can achieve liquid regeneration in lower temperature. When the solution and the air are in ''match'' state in collector/ regenerator, a match air to salt mass ratio ASMR* is found by theoretical study in which there is the largest theoretical storage capacity SC{sub max}. After two new concepts of the effective solution proportion (EPS) and the effective storage capacity (ESC) are defined, it is found by theoretical calculation that when ESP drops from 100% to 67%, ESC raises lowly, not drops and liquid outlet concentration C{sub str} {sub sol} increases from 40% to 49% in which its increment totals to 90%. All these data explain fully that air pretreatment liquid regeneration equipment enables to improve the performance of liquid desiccant cooling system. (orig.)
SAR image autofocus by sharpness optimization: a theoretical study.
Morrison, Robert L; Do, Minh N; Munson, David C
2007-09-01
Synthetic aperture radar (SAR) autofocus techniques that optimize sharpness metrics can produce excellent restorations in comparison with conventional autofocus approaches. To help formalize the understanding of metric-based SAR autofocus methods, and to gain more insight into their performance, we present a theoretical analysis of these techniques using simple image models. Specifically, we consider the intensity-squared metric, and a dominant point-targets image model, and derive expressions for the resulting objective function. We examine the conditions under which the perfectly focused image models correspond to stationary points of the objective function. A key contribution is that we demonstrate formally, for the specific case of intensity-squared minimization autofocus, the mechanism by which metric-based methods utilize the multichannel defocusing model of SAR autofocus to enforce the stationary point property for multiple image columns. Furthermore, our analysis shows that the objective function has a special separble property through which it can be well approximated locally by a sum of 1-D functions of each phase error component. This allows fast performance through solving a sequence of 1-D optimization problems for each phase component simultaneously. Simulation results using the proposed models and actual SAR imagery confirm that the analysis extends well to realistic situations.
Theoretical study of fractal growth and stability on surface
DEFF Research Database (Denmark)
Dick, Veronika V.; Solov'yov, Ilia; Solov'yov, Andrey V.
2009-01-01
We perform a theoretical study of the fractal growing process on surface by using the deposition, diffusion, aggregation method. We present a detailed analysis of the post-growth processes occurring in a nanofractal on surface. For this study we developed a method which describes the internal...... dynamics of particles in a fractal and accounts for their diffusion and detachment. We demonstrate that these kinetic processes are responsible for the formation of the final shape of the islands on surface after the post-growth relaxation....
Complex coacervation: A field theoretic simulation study of polyelectrolyte complexation
Lee, Jonghoon; Popov, Yuri O.; Fredrickson, Glenn H.
2008-06-01
Using the complex Langevin sampling strategy, field theoretic simulations are performed to study the equilibrium phase behavior and structure of symmetric polycation-polyanion mixtures without salt in good solvents. Static structure factors for the segment density and charge density are calculated and used to study the role of fluctuations in the electrostatic and chemical potential fields beyond the random phase approximation. We specifically focus on the role of charge density and molecular weight on the structure and complexation behavior of polycation-polyanion solutions. A demixing phase transition to form a ``complex coacervate'' is observed in strongly charged systems, and the corresponding spinodal and binodal boundaries of the phase diagram are investigated.
Theoretical study of fractal growth and stability on surface
DEFF Research Database (Denmark)
Dick, Veronika V.; Solov'yov, Ilia; Solov'yov, Andrey V.
2009-01-01
We perform a theoretical study of the fractal growing process on surface by using the deposition, diffusion, aggregation method. We present a detailed analysis of the post-growth processes occurring in a nanofractal on surface. For this study we developed a method which describes the internal...... dynamics of particles in a fractal and accounts for their diffusion and detachment. We demonstrate that these kinetic processes are responsible for the formation of the final shape of the islands on surface after the post-growth relaxation....
Ma, Zhongyun; Wang, Pu; Pei, Yong
2016-09-29
Based on the recently reported atomic structures of thiolate-protected Au28(SR)20, Au36(SR)24, Au44(SR)28, and Au52(SR)32 clusters, a family of homogeneous, linear, thiolate-protected gold superstructures containing novel quasi-face-centered-cubic (quasi-fcc) Au-cores is theoretically envisioned, denoted as the Au20+8N(SR)16+4N cluster. By means of density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations, a unified view of the geometric structure, electronic structure, magic stable size and size-dependent NIR absorption properties of Au20+8N(SR)16+4N clusters is provided. We find that the Au20+8N(SR)16+4N clusters demonstrate oscillating transformation energies dependent on N. The odd-N clusters show more favorable (negative) reaction energies than the even-N clusters. The magic stability of recently reported Au28(SR)20, Au36(SR)24, Au44(SR)28, Au52(SR)32 and Au76(SR)44 clusters can be addressed from the relative reaction energies and geometric distortion of Au-cores. A novel 4N + 4 magic electron-number is suggested for the Au20+8N(SR)16+4N cluster. Using the polyhedral skeletal electron pair theory (PSEPT) and the extended Hückel molecular orbital (EHMO) calculations, we suggest that the magic 4N + 4 electron number is correlated with the quasi-fcc Au-cores, which can be viewed as double helical tetrahedron-Au4 chains. The size-dependent optical absorption properties of Au20+8N(SR)16+4N clusters are revealed based on TD-DFT calculations. We propose that these clusters are potential candidates for the experimental synthesis of atomically precise one-dimensional ligand protected gold superstructures with tunable NIR absorption properties.
Gayathri, Kasirajan; Radhika, Ramachandran; Shankar, Ramasamy; Malathi, Mahalingam; Savithiri, Krishnaswamy; Sparkes, Hazel A.; Howard, Judith A. K.; Mohan, Palathurai Subramaniam
2017-04-01
A novel compound 2-chloro-3,6-bis-(quinolin-8-yloxymethyl)-quinoline 3 bearing a tri-quinoline moiety has been synthesized from 2-chloro-3,6-dimethyl quinoline 1 and 8-hydroxy quinoline 2 using dry acetone and K2CO3 as a base. 3 has been characterized by using FT-IR, FT-Raman, UV-Vis, 1H NMR, 13C NMR spectra and single crystal X-ray diffraction methods. We have also made a combined experimental and theoretical study on the molecular structure, vibrational spectra, NMR, FT-IR, FT-Raman and UV-Vis spectra of 2-chloro-3,6-bis-(quinolin-8-yloxymethyl)-quinoline. The theoretical studies of the title compound have been evaluated by using density functional theory calculations using B3LYP/6-31+G(d,p) and M06-2X/6-31+G(d,p) level of theories. The calculated theoretical values were found to be in good agreement with the experimental findings. The single crystal structure 3 crystallized in the orthorhombic space group Pna21. The compound 3 exhibits higher cytotoxicity in human cervical cancer cell lines (HeLa) than human breast cancer cell lines (MCF7).
Information-Theoretic Conditions for Two-Party Secure Function Evaluation
DEFF Research Database (Denmark)
Schaffner, Christian; Crépeau, Claude; Savvides, George
2006-01-01
The standard security definition of unconditional secure function evaluation, which is based on the ideal/real model paradigm, has the disadvantage of being overly complicated to work with in practice. On the other hand, simpler ad-hoc definitions tailored to special scenarios have often been...... flawed. Motivated by this unsatisfactory situation, we give an information-theoretic security definition of secure function evaluation which is very simple yet provably equivalent to the standard, simulation-based definitions....
Information-Theoretic Conditions for Two-Party Secure Function Evaluation
DEFF Research Database (Denmark)
Schaffner, Christian; Crépeau, Claude; Savvides, George
2006-01-01
The standard security definition of unconditional secure function evaluation, which is based on the ideal/real model paradigm, has the disadvantage of being overly complicated to work with in practice. On the other hand, simpler ad-hoc definitions tailored to special scenarios have often been...... flawed. Motivated by this unsatisfactory situation, we give an information-theoretic security definition of secure function evaluation which is very simple yet provably equivalent to the standard, simulation-based definitions....
Digernes, Ingrid; Bjørnerud, Atle; Vatnehol, Svein Are S; Løvland, Grete; Courivaud, Frédéric; Vik-Mo, Einar; Meling, Torstein R; Emblem, Kyrre E
2017-06-01
Mapping the complex heterogeneity of vascular tissue in the brain is important for understanding cerebrovascular disease. In this translational study, we build on previous work using vessel architectural imaging (VAI) and present a theoretical framework for determining cerebral vascular function and heterogeneity from dynamic susceptibility contrast magnetic resonance imaging (MRI). Our tissue model covers realistic structural architectures for vessel branching and orientations, as well as a range of hemodynamic scenarios for blood flow, capillary transit times and oxygenation. In a typical image voxel, our findings show that the apparent MRI relaxation rates are independent of the mean vessel orientation and that the vortex area, a VAI-based parameter, is determined by the relative oxygen saturation level and the vessel branching of the tissue. Finally, in both simulated and patient data, we show that the relative distributions of the vortex area parameter as a function of capillary transit times show unique characteristics in normal-appearing white and gray matter tissue, whereas tumour-voxels in comparison display a heterogeneous distribution. Collectively, our study presents a comprehensive framework that may serve as a roadmap for in vivo and per-voxel determination of vascular status and heterogeneity in cerebral tissue.
Theoretical studies of ionic conductivity of crosslinked chitosan membranes
Energy Technology Data Exchange (ETDEWEB)
Chavez, Ernesto Lopez [Programa de Ingenieria Molecular y Nuevos Materiales, Universidad Autonoma de la Ciudad de Mexico, Fray Servando Teresa de Mier 92, 1er. Piso, Col Centro, Mexico D.F. CP 06080 (Mexico); Oviedo-Roa, R.; Contreras-Perez, Gustavo; Martinez-Magadan, Jose Manuel [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas Norte 152, Col. San Bartolo Atepehuacan, CP 07730 Mexico D.F. (Mexico); Castillo-Alvarado, F.L. [Escuela Superior de Fisica y Matematicas del Instituto Politecnico Nacional, Edificio 9 de la UPALM, Colonia Lindavista, Mexico D.F. CP 07738 (Mexico)
2010-11-15
Ionic conductivity of crosslinked chitosan membranes was studied using techniques of molecular modeling and simulation. The COMPASS force field was used. The simulation allows the description of the mechanism of ionic conductivity along the polymer matrix. The theoretical results obtained are compared with experimental results for chitosan membranes. The analysis suggests that the conduction mechanism is portrayed by the overlapping large Polaron tunneling model. In addition, when the chitosan membrane was crosslinked with an appropriate degree of crosslinking its ionic conductivity, at room temperature, was increased by about one order of magnitude. The chitosan membranes can be used as electrolytes in solid state batteries, electric double layer capacitors and fuel cells. (author)
Theoretical Study of 1,8-Diaminonaphthalene Polymerization
Nateghi, Mohammad R.; Kalantari, F.
2007-12-01
The polymerization of 1,8-diaminonaphthalene (1,8-DAN) was studied by a theoretical approach based on Hartree-Fock calculations. Investigation of relative stability of most possible dimers, trimers and tetramers yields very useful data concerning the regioselectivity of the coupling reaction as well as the final structures of the polymeric chains. The mechanism is more likely to occur via a radical-radical pathway and leads to mixture of compounds through ortho-C-C and para-C-N linkages.
Theoretical Neuroanatomy:Analyzing the Structure, Dynamics,and Function of Neuronal Networks
Seth, Anil K.; Edelman, Gerald M.
The mammalian brain is an extraordinary object: its networks give rise to our conscious experiences as well as to the generation of adaptive behavior for the organism within its environment. Progress in understanding the structure, dynamics and function of the brain faces many challenges. Biological neural networks change over time, their detailed structure is difficult to elucidate, and they are highly heterogeneous both in their neuronal units and synaptic connections. In facing these challenges, graph-theoretic and information-theoretic approaches have yielded a number of useful insights and promise many more.
Theoretical studies of lipid bilayer electroporation using molecular dynamics simulations
Levine, Zachary Alan
Computer simulations of physical, chemical, and biological systems have improved tremendously over the past five decades. From simple studies of liquid argon in the 1960s to fully atomistic simulations of entire viruses in the past few years, recent advances in high-performance computing have continuously enabled simulations to bridge the gap between scientific theory and experiment. Molecular dynamics simulations in particular have allowed for the direct observation of spatial and temporal events which are at present inaccessible to experiments. For this dissertation I employ all-atom molecular dynamics simulations to study the transient, electric field-induced poration (or electroporation) of phospholipid bilayers at MV/m electric fields. Phospholipid bilayers are the dominant constituents of cell membranes and act as both a barrier and gatekeeper to the cell interior. This makes their structural integrity and susceptibility to external perturbations an important topic for study, especially as the density of electromagnetic radiation in our environment is increasing steadily. The primary goal of this dissertation is to understand the specific physical and biological mechanisms which facilitate electroporation, and to connect our simulated observations to experiments with live cells and to continuum models which seek to describe the underlying biological processes of electroporation. In Chapter 1 I begin with a brief introduction to phospholipids and phospholipid bilayers, followed by an extensive overview of electroporation and atomistic molecular dynamics simulations. The following chapters will then focus on peer-reviewed and published work we performed, or on existing projects which are currently being prepared for submission. Chapter 2 looks at how external electric fields affect both oxidized and unoxidized lipid bilayers as a function of oxidation concentration and oxidized lipid type. Oxidative damage to cell membranes represents a physiologically relevant
Chochos, Christos L; Avgeropoulos, Apostolos; Lidorikis, Elefterios
2013-02-14
The theoretical estimation of energy levels and energy gaps of conjugated polymers for organic photovoltaics (OPVs) represents in principle a useful tool for the prescreening of new donor systems as a suitable pair for the fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM). In this study, ten tetraphenyl-substituted indacenodithiophene (IDT) copolymers (eight in the form of donor-acceptor), whose energy gaps vary in the range of 1.48-2.11 eV have been selected and their highest occupied molecular orbitals (HOMOs), lowest unoccupied molecular orbitals (LUMOs), and gap energies have been calculated by applying density functional theory (DFT) and/or time-dependent density functional theory (TD-DFT) methods. In spite of the examined molecular structure variety, nice correlations (theoretical models) between experimental and theoretical electronic parameters were found. It is shown that the theoretical band gap estimated by the TD-DFT using dimer model compounds and DFT using tetramer model compounds provide in good agreement the optical band gap of these polymers. Finally, the optimum theoretical limits of the LUMO offset between the fullerene and the IDT tetramer model compounds, for which high performance OPVs (efficiency > 6%) are obtained, is presented for the first time.
THEORETICAL ANALYSIS STUDY OF FORMATION OF FUTURE LEGAL LAWYERS
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Eugene Stepanovich Shevlakov
2015-09-01
Full Text Available The article deals with topical issues of formation of legal consciousness of future lawyers in high school. Obtained kinds of legal consciousness of future lawyers, determined its structure. Dedicated components of justice are mutually reinforcing, and provide an opportunity for further development of the personality of the future specialist, their personal growth.The purpose: to carry out theoretical analysis of the problem of formation of legal consciousness of future lawyers.The novelty is based. On the analysis of theoretical appro-aches of pedagogy, psychology, law, the notion of «lawfulness of the future of the law student», which is regarded as a form of social consciousness, which is a set of legal views and feelings, expressing the attitude to the law and legal phenomena that have regulatory in character and which includes know-ledge of legal phenomena and their evaluation from the point of view of fairness and justice, formed in the process of studying in the University.Results: this article analyzes different approaches to understanding the content and essence of the concept of legal consciousness of the legal profession. Define the types and structure of legal consciousness of future lawyers.
Phototransformations of quinaldic acid: Theoretical and experimental study
Shterev, Ivan G.; Delchev, Vassil B.
2017-01-01
A combined theoretical and experimental study was performed in order to clarify the mechanisms of phototransformations of a quinaldic acid solution in acetonitrile when exposed to UV radiation. The theoretical calculations were performed at the BLYP/aug-cc-pVDZ level. It was established that the most stable isomer of the compound in the solution is the one with an intramolecular H-bond between the H atom from the carboxylic group and the N atom from the quinoline ring. The major photoprocess is the breaking of the intramolecular H-bond, i.e. the rotation around the Csbnd OH bond of the carboxylic group through the specroscopically active 1ππ* excited state. Rietveld method was applied to refine the crystal structure of the compound. The refinement lead to the following unit cell parameters: a = 9.76754 Å, b = 6.02724 Å, c = 28.11714 Å, β = 90.495°; and a space Group of P 2/c (Z = 4). The cell volume is 1655.23 Å3.
Theoretical study of ionization potentials of N-heterocyclic compounds
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Liudmyla K. Sviatenko
2014-12-01
Full Text Available The ability to predict the redox properties is an important tool for study electron transfer processes occurring in the gas-phase (atmospheric chemistry or in the condensed phase (electrochemistry, biochemistry. MPWB1K/6-31+G(d and MPWB1K/tzvp theoretical models were found to provide reasonable accuracy of the prediction of ionization potentials for mono- and polycyclic azacompounds. The root mean square errors of the methods are 0.19 and 0.20, respectively. While the mean absolute deviation for both methods is the same and equals to 0.15 eV. These theoretical models were applied to predict ionization potentials for compounds not evaluated experimentally. Influence of substitutes and a number of nitrogen atoms on value of ionization potential was analyzed. Methyl-, and phenyl- groups, and fused benzo cycle decrease ionization potentials of N-heterocycles. Increase of amount of nitrogen atoms in five-membered cycles leads to significant enlargement of ionization potentials.
Theoretical Study on Sulfur Dioxide Absorption with Citrate Solution
Institute of Scientific and Technical Information of China (English)
薛娟琴; 洪涛; 王召启; 李林波
2006-01-01
The citrate absorption of SO2 is currently one of the most successful and economic methods to harness sulfur dioxide pollution.In order to theoretically elucidate the mechanism of SO2 absorption by citrate solution and provide theoretical instruction for experiments and industrial process, the theory of multi-buffer solution, combined with computer numerical calculation methods, was applied to study the distribution parameters of the components of the citrate solution in the process of SO2 absorption and the following results were obtained: (1) HCi2- and H2Ci- in the citrate solution played the dominant role in the absorption and desorption processes; (2) Through the calculation for the buffer capacity of citrate solution, it was found that the pH of the absorption and desorption solution should be in the range of 2～8, while at pH=4.5 the buffer capacity reached its maximum. Some valuable parameters were obtained, which are instructive to the ensuing experiments and industrial design.
Frequencies Shift in Relativistic Binary System (Theoretical Study)
El Fady Morcos, Abd
2016-07-01
A generalized formula for Kermack, McCrea and Whittaker (KMW), has been derived by the author and et al., to study the limb effect of massive rapidly rotating stars. In this work a modified Curzon exact solution for Einstein's field equations has been used to study the variation in the frequencies of signals' carriers from a relativistic binary system. The primary star is assumed to be massive with respect to the secondary one. The center of mass is considered to be coincident to the center of rotating polar coordinate system. The rotation of the secondary star around the primary star and Earth's observer rotates with the Earth are considered in our calculation. A general theoretical formula for the variation in the frequencies of the signals' carriers from a binary system is obtained
Ahmadnezhad, M.; Darvish Ganji, M.; Rezvani, M.
2015-11-01
Functionalization of carbon nanotube (CNT) with multiple redox and photo active entities is one of the extensive processes due to its importance in building molecular or supramolecular electronic devices, solar energy storage and conversion systems. Thus, to have better understanding about structural aspects and correct electronic structure of these large systems, the quantum studies have gained increased popularity. In present study, we have investigated the structural and electronic properties of functionalized CNTs (fCNTs) with [Ru(bpy)2(5-NH2-1,10-phen)]+2, (Ru-bpy-phen)+2, supramolecule based on DFT calculations. Main attention has been applied to obtain stable configuration, binding energies and effect of functionalization on electronic behavior of the selected supramolcule. We also evaluate the effect of nanotube's diameter and chirality on electronic properties of considered supramolecule. Calculated binding energies show that interaction between the (Ru-bpy-phen)+2 and the host CNTs depends on the tube diameter while the chirality doesn't affect significantly on the binding nature of respected complex. We have also investigated the influence of non-local dispersion interactions (vdW) and temperature on the stability and electronic structure of the considered system. Results obtained from the ab initio MD simulations showed that increasing the temperature can affect the distance between C and N atoms in the linkage position. The charge analysis indicates the existence of remarkable charge transfer between (Ru-bpy-phen)+2 as donor and fCNTs as acceptor moieties in the isolated molecule. In the presence of vdW forces and at higher temperature, the charge transfer was decreased but the direction of transferred charge remains unchanged.
Theoretical study of magnetoelectric effects in noncentrosymmetric and cuprate superconductors
Kashyap, Manoj K.
A century after the discovery of superconductivity at the lab of Kamerlingh Onnes in 1911, it is noticeable that the phenomenon is quite ubiquitous in nature. In addition to a long list of superconducting alloys and compounds, almost half the elements in the periodic table superconduct. By the late seventies, superconductivity was thought to be well understood. This turned out to be a myth, with the discovery of unconventional superconductors that defied Bardeen-Cooper-Schrieffer (BCS) theory. Cuprates have been the most prominent example among them ever since their discovery in 1986 by Bednorz and Muller. Another example of non-compliance with BCS theory lie among noncentrosymmetric superconductors. In this dissertation, magnetoelectric (ME) effects in these two classes of superconductors have been studied from different perspectives, utilizing Ginzburg-Landau (GL) theory. Even though GL theory was proposed before the BCS theory, it was not given much importance due to its phenomenological nature until Gor'kov proved that it is a limiting form of the microscopic BCS theory. However today, in the absence of any complete microscopic theory to explain superconductivity in unconventional superconductors, Ginzburg-Landau theory is an important tool to move ahead and qualitatively understand the behavior of varied superconducting systems. Noncentrosymmetric superconductors have generated much theoretical interest since 2004 despite been known for long. The absence of inversion symmetry in non- centrosymmetric superconductors allows for extra terms called Lifshitz invariants in the Ginzburg-Landau functional. This leads to magnetoelectric effects that do not exist in centrosymmetric superconductors. One manifestation of this is in the vortex structure in materials with a cubic point group O. In particular, a current is predicted to flow parallel to the applied magnetic field in such a vortex in addition to the usual vortex supercurrents. In this work, we present both
Theoretical study on the band structure and optical properties of 4H-SiC
Institute of Scientific and Technical Information of China (English)
Xu Peng-Shou; Xie Chang-Kun; Pan Hai-Bin; Xu Fa-Qiang
2004-01-01
We have studied the band structure and optical properties of 4H-SiC by using a full potential linearized augmented plane waves (FPLAPW) method. The density of states (DOS) and band structure are presented. The imaginary part of the dielectric function has been obtained directly from the band structure calculation. With band gap correction, the real part of the dielectric function has been derived from the imaginary part by the Kramers-Kronig (KK) dispersion relationship. The values of reflectivity for normal incidence as a function of photon energy have also been calculated.We found the theoretical results are in good agreement with the experimental data.
Theoretical study of the thermal decomposition of dimethyl disulfide.
Vandeputte, Aäron G; Reyniers, Marie-Françoise; Marin, Guy B
2010-10-07
Despite its use in a wide variety of industrially important thermochemical processes, little is known about the thermal decomposition mechanism of dimethyl disulfide (DMDS). To obtain more insight, the radical decomposition mechanism of DMDS is studied theoretically and a kinetic model is developed accounting for the formation of all the decomposition products observed in the experimental studies available in literature. Thermochemical data and rate coefficients are obtained using the high-level CBS-QB3 composite method. Among five methods tested (BMK/6-311G(2d,d,p), MPW1PW91/6-311G(2d,d,p), G3, G3B3, and CBS-QB3), the CBS-QB3 method was found to reproduce most accurately the experimental standard enthalpies of formation for a set of 17 small organosulfur compounds and the bond dissociation energies for a set of 10 sulfur bonds. Enthalpies of formation were predicted within 4 kJ mol(-1) while the mean absolute deviation on the bond dissociation enthalpies amounts to 7 kJ mol(-1). From the theoretical study, a new reaction path is identified for the formation of carbon disulfide via dithiirane (CH(2)S(2)). A reaction mechanism was constructed containing 36 reactions among 25 species accounting for the formation of all the decomposition products reported in literature. High-pressure limit rate coefficients for the 36 reactions in the reaction mechanism are presented. The kinetic model is able to grasp the experimental observations. With the recombination of thiyl radicals treated as being in the low-pressure limit, the experimentally reported first-order rate coefficients for the decomposition of DMDS are reproduced within 1 order of magnitude, while the observed product selectivities of most compounds are reproduced satisfactory. Simulations indicate that at high conversions most of the carbon disulfide forms according to the newly identified reaction path involving the formation of dithiirane.
Experimental and theoretical study of metal combustion in oxygen flows
El-Rabii, Hazem; Muller, Maryse
2016-01-01
The effects of oxygen flow speed and pressure on the iron and mild steel combustion are investigated experimentally and theoretically. The studied specimens are vertical cylindrical rods subjected to an axial oxygen flow and ignited at the upper end by laser irradiation. Three main stages of the combustion process have been identified experimentally: (1) Induction period, during which the rod is heated until an intensive metal oxidation begins at its upper end; (2) Static combustion, during which a laminar liquid "cap" slowly grows on the upper rod end; and, after the liquid cap detachment from the sample, (3) Dynamic combustion, which is characterized by a rapid metal consumption and turbulent liquid motions. An analytical description of these stages is given. In particular, a model of the dynamic combustion is constructed based on the turbulent oxygen transport through the liquid metal-oxide flow. This model yields a simple expression for the fraction of metal burned in the process, and allows one to calcul...
Theoretical study on alkaline hydrolysis of trinitrotoluene: later steps
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Liudmyla K. Sviatenko
2015-10-01
Full Text Available Alkaline hydrolysis is an effective method to destroy such the pollutant as 2,4,6-trinitrotoluene (TNT in solution and in well-mixed soil. The mechanism of hydrolytic transformation of polynegative complex, which is one of the products of early stages of TNT hydrolysis, was theoretically investigated at the SMD(Pauling/M06-2X/6-31+G(d,p level under alkali condition. The studied process consists of more than twenty steps and includes a six-membered cycle cleavage and sequenced [1,3]-hydrogen migration and C-C bond rupture. The highest energy barrier is observed for interaction of nitromethanide with hydroxide. The most exothermic steps are C–C bonds breaking. As a result final products such as formate, acetate, ammonium, and nitrogen are formed.
Field-Theoretic Studies of Nanostructured Triblock Polyelectrolyte Gels
Audus, Debra; Fredrickson, Glenn
2012-02-01
Recently, experimentalists have developed nanostructured, reversible gels formed from triblock polyelectrolytes (Hunt et al. 2011, Lemmers et al. 2010, 2011). These gels have fascinating and tunable properties that reflect a heterogeneous morphology with domains on the order of tens of nanometers. The complex coacervate domains, aggregated oppositely charged end-blocks, are embedded in a continuous aqueous matrix and are bridged by uncharged, hydrophilic polymer mid-blocks. We report on simulation studies that employ statistical field theory models of triblock polyelectrolytes, and we explore the equilibrium self-assembly of these remarkable systems. As the charge complexation responsible for the formation of coacervate domains is driven by electrostatic correlations, we have found it necessary to pursue full ``field-theoretic simulations'' of the models, as opposed to the familiar self-consistent field theory approach. Our investigations have focused on morphological trends with mid- and end-block lengths, polymer concentration, salt concentration and charge density.
Theoretical study of irradiation effects in close binaries
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Srinivasa Rao M.
2009-01-01
Full Text Available The effect of irradiation is studied in a close binary system assuming that the secondary component is a point source, moving in a circular orbit. The irradiation effects are calculated on the atmosphere of the primary component in a 3-dimensional Cartesian coordinate geometry. In treating the reflection effect theoretically, the total radiation (ST is obtained as the sum of the radiation of 1 the effect of irradiation on the primary component which is calculated by using one dimensional rod model (Sr and 2 the self radiation of the primary component which is calculated by using the solution of radiative transfer equation in spherical symmetry (Ss. The radiation field is estimated along the line of sight of the observer at infinity. It is shown how the radiation field changes depending on the position of the secondary component.
Theoretical Study of Irradiation Effects in Close Binaries
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Srinivasa Rao, M.
2009-06-01
Full Text Available The effect of irradiation is studied in a close binary systemassuming that the secondary component is a point source, moving in a circularorbit. The irradiation effects are calculatedon the atmosphere of the primary component in a 3-dimensional Cartesiancoordinate geometry. In treating the reflection effect theoretically, the totalradiation $(S_mathrm{T}$ is obtained as the sum of the radiation of 1 the effect ofirradiation on the primary component which is calculated by using onedimensional rod model $(S_mathrm{r}$ and 2 the self radiation of the primarycomponent which is calculated by using the solution of radiative transferequation in spherical symmetry $(S_mathrm{s}$. The radiation field is estimated alongthe line of sight of the observer at infinity. It is shown how the radiationfield changes depending on the position of the secondary component.
A theoretical study on ascorbic acid dissociation in water clusters.
Demianenko, Eugeniy; Ilchenko, Mykola; Grebenyuk, Anatoliy; Lobanov, Victor; Tsendra, Oksana
2014-03-01
Dissociation of ascorbic acid in water has been studied by using a cluster model. It was examined by density functional theory (DFT) with the В3LYP, M06, and wB97XD functionals and a 6-311++G(d,p) basis set. The thermodynamic and kinetic characteristics of proton transfer from ascorbic acid molecule to water clusters were calculated as well as the equilibrium constants (pK a ) for the related processes. The used functionals in the DFT method together with continuum solvent models provided results close to the experimental data for the dissociation constant of ascorbic acid in aqueous solution.
Theoretical and Numerical Study of Nonlinear Phononic Crystals
Guerder, Pierre-Yves
This work is dedicated to the theoretical and numerical study of nonlinear phononic crystals. The studied nonlinearities are those due to the second (quadratic) and third (cubic) order elastic constants of the materials that constitute the crystals. Nonlinear effects are studied by the means of finite element methods, used to simulate the propagation of an elastic wave through the crystals. A first research project concerns the study of a bone structure, namely the dispersion of elastic waves in a structure composed of collagen and hydroxy apatite alternate constituent layers. Simulations showed that it exists a strong link between bones hydration and their ability to dissipate the energy. The second study relates to an elastic resonator. A structure composed of steel inclusions in a silica matrix shows a switch behavior when the cubic nonlinearities of steel are taken into account. This strong nonlinear effect appears when the amplitude of the incident wave reaches a threshold. A full analytical model is provided. The last study demonstrates the design of composite materials with both strong cubic nonlinearities and weak quadratic nonlinearities. The derivation of the mixing laws of the elastic parameters of a nonlinear material inside a linear one is performed up to order three. Equations show a strong amplification of the nonlinear parameters of the material for some concentrations. Numerical simulations allow to conclude that the above mentioned resonator can be produced.
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V.V. Lutsiak
2014-06-01
Full Text Available The aim of the article. Entrepreneurship is a sector of the market economic system that ensures satisfaction of social needs and fills the market with goods and services. The role of small business in the economic system of Ukraine is that this form of entrepreneurship is regarded as a factor that forms the competitive environment, which in its turn promotes a healthy market economy. Further development and elaboration of theoretical and methodological basics of small enterprises marketing activity requires constant attention with taking into consideration changes in the global market environment. The purpose of this research is the analysis of actual understanding of business, identification of main theoretical and methodological tasks aimed to ensure the effective functioning of enterprises in the context of marketing activity organization and realization. This paperwork resolves a number of issues in business content research and identifies the key targets of marketing activity of a company. The results of the analysis. The study was conducted with the use of system analysis elements, including historical and objective description of entrepreneurship as a factor of organizational basis of enterprise. This paperwork researches the genesis and the historical development of «entrepreneurship» as a substantive category. It also analyzes the basic characteristics that have been acquired by entrepreneurship in today's market environment. Entrepreneurship can be designated by following features: freedom, aspiration for success, risk, innovativeness, social responsibility, activity, initiative, social transformation. Activity, independence, aspiration for success and initiative of entrepreneurship are subject to the influence of political, legal and social-cultural environment. These circumstances cause the objective necessity of monitoring of the legislation that regulates business. The degree of risk in the entrepreneurship is associated with the
A study of brain networks associated with swallowing using graph-theoretical approaches.
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Bo Luan
Full Text Available Functional connectivity between brain regions during swallowing tasks is still not well understood. Understanding these complex interactions is of great interest from both a scientific and a clinical perspective. In this study, functional magnetic resonance imaging (fMRI was utilized to study brain functional networks during voluntary saliva swallowing in twenty-two adult healthy subjects (all females, [Formula: see text] years of age. To construct these functional connections, we computed mean partial correlation matrices over ninety brain regions for each participant. Two regions were determined to be functionally connected if their correlation was above a certain threshold. These correlation matrices were then analyzed using graph-theoretical approaches. In particular, we considered several network measures for the whole brain and for swallowing-related brain regions. The results have shown that significant pairwise functional connections were, mostly, either local and intra-hemispheric or symmetrically inter-hemispheric. Furthermore, we showed that all human brain functional network, although varying in some degree, had typical small-world properties as compared to regular networks and random networks. These properties allow information transfer within the network at a relatively high efficiency. Swallowing-related brain regions also had higher values for some of the network measures in comparison to when these measures were calculated for the whole brain. The current results warrant further investigation of graph-theoretical approaches as a potential tool for understanding the neural basis of dysphagia.
THEORETICAL STUDY OF THE ABSORPTION SPECTRA OF TRIAMTERENE
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M. Ramegowda
2013-03-01
Full Text Available ABSTRACT: Time dependent density functional theory (TDDFT calculations have been carried out to study the electronic structure and the UV absorption spectra of Triamterene. The UV spectra have been investigated with inclusion of solvent effect. The B3LYP functional with a 6-31G(d, p basis sets have been used to compute absorption energies. The solvent effects have been described within the polarizable continuum model (PCM. The geometries are optimized using density functional theory (DFT with B3LYP functional combined with 6-31G(d, p basis sets. The vertical absorption energies both in gas phase and in polar solvents such as ethanol, methanol and water were computed. Red-shift of the absorption maximum in the polar solvents is discussed in terms of electrostatic interaction energy, oscillator strength and dipole moment.
Studies of Chinese speakers with dysarthria: informing theoretical models.
Whitehill, Tara L
2010-01-01
Most theoretical models of dysarthria have been developed based on research using individuals speaking English or other Indo-European languages. Studies of individuals with dysarthria speaking other languages can allow investigation into the universality of such models, and the interplay between language-specific and language-universal aspects of dysarthria. In this article, studies of Cantonese- and Mandarin-Chinese speakers with dysarthria are reviewed. The studies focused on 2 groups of speakers: those with cerebral palsy and those with Parkinson's disease. Key findings are compared with similar studies of English speakers. Since Chinese is tonal in nature, the impact of dysarthria on lexical tone has received considerable attention in the literature. The relationship between tone [which involves fundamental frequency (F(0)) control at the syllable level] and intonation (involving F(0) control at the sentential level) has received more recent attention. Many findings for Chinese speakers with dysarthria support earlier findings for English speakers, thus affirming the language-universal aspect of dysarthria. However, certain differences, which can be attributed to the distinct phonologies of Cantonese and Mandarin, highlight the language-specific aspects of the condition.
Multi-Nucleon Short-Range Correlation Model for Nuclear Spectral Functions: I. Theoretical Framework
Artiles, Oswaldo
2016-01-01
We develop a theoretical approach for nuclear spectral functions at high missing momenta and removal energy based on the multi-nucleon short-range correlation~(SRC) model. The approach is based on the effective Feynman diagrammatic method which allows to account for the relativistic effects important in the SRC domain. In addition to two-nucleon SRC with center of mass motion we derived also the contribution of three-nucleon SRCs to the nuclear spectral functions. The latter is modeled based on the assumption that 3N SRCs are a product of two sequential short range NN interactions. This approach allowed us to express the 3N SRC part of the nuclear spectral function as a convolution of two NN SRCs. Thus the knowledge of 2N SRCs allows us to model both two- and three-nucleon SRC contribution to the spectral function. The derivations of the spectral functions are based on the two theoretical frameworks in evaluating covariant Feynman diagrams: In the first, referred as virtual nucleon approximation, we reduce Fe...
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Xiaojin Li
2013-01-01
Full Text Available Previous studies have investigated both structural and functional brain networks via graph-theoretical methods. However, there is an important issue that has not been adequately discussed before: what is the optimal theoretical graph model for describing the structural networks of human brain? In this paper, we perform a comparative study to address this problem. Firstly, large-scale cortical regions of interest (ROIs are localized by recently developed and validated brain reference system named Dense Individualized Common Connectivity-based Cortical Landmarks (DICCCOL to address the limitations in the identification of the brain network ROIs in previous studies. Then, we construct structural brain networks based on diffusion tensor imaging (DTI data. Afterwards, the global and local graph properties of the constructed structural brain networks are measured using the state-of-the-art graph analysis algorithms and tools and are further compared with seven popular theoretical graph models. In addition, we compare the topological properties between two graph models, namely, stickiness-index-based model (STICKY and scale-free gene duplication model (SF-GD, that have higher similarity with the real structural brain networks in terms of global and local graph properties. Our experimental results suggest that among the seven theoretical graph models compared in this study, STICKY and SF-GD models have better performances in characterizing the structural human brain network.
Theoretical Study of Spin Crossover in 30 Iron Complexes
DEFF Research Database (Denmark)
Kepp, Kasper Planeta
2016-01-01
Spin crossover was studied in 30 iron complexes using density functional theory to quantify the direction and magnitude of dispersion, relativistic effects, zero-point energies, and vibrational entropy. Remarkably consistent entropy−enthalpy compensation was identified. Zero-point energies favor ...
Theoretical and experimental studies of 3β-acetoxy-5α-cholestan-6-one oxime
Khan, Azhar U.; Avecillia, Fernando; Malik, Nazia; Khan, Md. Shahzad; Khan, Mohd Shahid; Mushtaque, Md.
2016-10-01
Steroidal oxime (3β-acetoxy-5α-cholestan- 6-one oxime) has been synthesized using microwave-induced reaction in 3.5 min using saturated steroidal ketone and aqueous hydroxylamine hydrochloride in ethanol. The structure of the compound was elucidated by UV, IR, 1H NMR and X-ray single crystal structure. The computational quantum chemical studies like, IR, UV analysis were performed by density functional theory (DFT) at Becke-3-Lee-Yang-Parr(B3LYP) exchange-correlation functional in combination with 6-31++G(d,p) basis sets. The harmonic vibrational frequencies, the optimized geometric parameters have been interpreted and compared with experimental values. Theoretical wavelength at 214.88 cm-1 correspond to the experimental value 214.0 cm-1. The nature of this transition is n → π*. The theoretical results are in good agreement with experiment results.
A Theoretical Study on Reductive Debromination of Polybrominated Diphenyl Ethers
Directory of Open Access Journals (Sweden)
Xian-Fei Huang
2012-07-01
Full Text Available Recent progress has been made in the reductive debromination of polybrominated diphenyl ethers (PBDEs by nanoscale zero-valent iron (nZVI. To better understand the mechanism of this reaction, seven selected BDE congeners and their anions were investigated at the density functional theory (DFT level using four different methods, including B3LYP/6-31G(d, B3LYP/6-31+G(d, B3LYP/6-31G(d,p and B3LYP/6-311G(d,p. The cleaved C–Br bonds observed in the equilibrium structures of anionic PBDEs were adopted as the probe of the susceptible debromination position of PBDEs in the presence of nZVI, and the proposed major reaction pathways based on our calculations can satisfactorily conform to the reported experimental results. The debromination preference is theoretically evaluated as meta-Br > ortho-Br > para-Br. In addition, both the calculated frontier orbital energies and adiabatic electronic affinities were found to be highly related to their experimental reductive debromination rate constants. The highest linear regression coefficient was observed in the case using the energy of lowest unoccupied molecular orbital as the molecular descriptor obtained from B3LYP/6-31G(d (R^{2} = 0.961, n = 7 or B3LYP/6-31G(d,p (R^{2} = 0.961, n = 7. The results clearly showed the evidence of an electron transfer mechanism associated with this reductive debromination reaction.
Theoretical spectroscopic study of protonated and deuteronated PAHs
Buragohain, Mridusmita; Pathak, Amit
The study of Polycyclic Aromatic Hydrocarbon (PAH) plays a key role to understand astrophysical environments as they are ubiquitous in the Interstellar Medium (ISM). They account for about 5-10% of carbon budget in the universe and are responsible for the strong IR emission features at 3.3, 6.2, 7.7, 8.6, 11.2 and 12.7mum seen towards most of the interstellar objects including HII regions, reflection nebulae, planetary nebulae, late-type stars, as well as active star-forming regions. These IR features result from the relaxation of vibrationally excited PAHs. As PAHs are stable enough to survive the interstellar conditions, they could possibly be responsible for the enigmatic Diffuse Interstellar Bands (DIBs) which are optical absorption features on the interstellar extinction curve. The fact that interstellar PAHs are more likely to be ions has motivated the study of radical PAHs. Protonated PAHs formed by H(+) addition to neutral parent molecules, denoted as HPAH(+) , are an important form of closed shell PAH cation. Protonated forms show electronic transitions in the visible part of the spectrum where most DIBs are present, whereas neutral forms generally show their strongest electronic transitions in the UV region. We also report quantum chemical calculations on HPAH(+) and DPAH(+) (D(+) attached to PAH) to get the electronic and IR spectra to understand the IR emission and DIB features. A comparison of theoretical spectra with the available experimental spectra has also been carried out.
Directory of Open Access Journals (Sweden)
Álvaro Seiça
2012-12-01
Full Text Available In this essay I introduce the notion of transducer function in the fields of electronic literature and digital art. Firstly, I survey the transduction concept throughout its history in such domains as physics, genetics, microbiology, biochemistry, physiology, psychology, philosophy, logic and computer science. Secondly, I discuss the relevance of a transduction theory versus the advantage of a transducer function. I migrate the transduction concept into the fields of electronic literature and digital art, showcasing the contexts of application, and several transfer processes and functions. Finally, I apply the transducer function as a theoretical typology and a recognizable system, highlighting some artworks by R. Luke DuBois, André Sier and Scott Rettberg that can be read within this framework. Thus, it means taking into account a set of transfer and conversion processes: information, patterns and data among mechanisms, technologies, themes, creative and theoretical guidelines. In this sense, I develop a critical framework that operates as a method for analyzing and comprehend further digital artworks.
a correlational study of students 'theoretical and practical ...
African Journals Online (AJOL)
Galadanci & Mukhtar
Moment Correlation Coefficient, the Coefficients of Correlation obtained are ... students' understanding of subjects/courses that have been taught to ... Literature Review ... the theoretical and practical scores of students in some basic science ...
Theoretical Study of Elastic Properties of Tungsten Disilicide
Institute of Scientific and Technical Information of China (English)
XU Guo-Liang; ZHANG Dong-Ling; XIA Yao-Zheng; LIU Xue-Feng; LIU Yu-Fang; ZHANG Xian-Zhou
2009-01-01
@@ The plane-wave pseudopotential method using the generalized gradient approximation within the framework of density functional theory is applied to analyse the lattice parameters, elastic constants, bulk moduli, shear moduli and Young's moduli of WSi2. The quasi-harmonic Debye model, using a set of total energy versus cell volume obtained with the plane-wave pseudopotential method, is applied to the study of the elastic properties and vibrational effects. The athermal elastic constants of WSi2 are calculated as a function of pressure up to 35 GPa. The relationship between bulk modulus and temperature up to 1200K is also obtained. Moreover, the Debye temperature is determined from the non-equilibrium Gibbs function. The calculated results are in good agreement with the experimental data.
Three theoretical studies of ferroelectric materials in different geometries
Palova, Lucia
Using a combination of numerical and analytical techniques, I present characterizations of ferroelectric materials in bulk, thin-film and nanostructure geometries. My results have impact on ongoing research and on design for nanodevices. Size-dependent effects in ferroelectrics are important due to their long-range electrostatic interactions; thus their dielectric properties depend on electromechanical boundary conditions. In my first study, I address the effects of strain on the measured properties of thin-film (TF) ferroelectrics. It has been suggested that the observed suppression of many TF dielectric characteristics implies underlying strain gradients in the film. I show that the same effects can be explained by a simpler model with homogeneous strain, and I suggest a "smoking gun" benchtop probe. The quantum paraelectric-ferroelectric transition (QPFT) is the topic of my second study. Using methods including finite-size scaling and self-consistent Gaussian theory, I calculate the classical-quantum crossover in the dielectric susceptbility and the resulting temperature-pressure phase diagram; comparison with current experiment is excellent and predictions are made for future measurements. Here, temperature can be considered a "finite-size effet" in time, and previous results on the QPFT using diagrammatic techniques are recovered and extended using this approach. Recent synthesis of artificially structured oxides with "checkerboard" patterning at the nanoscale has been reported, and this serves as motivation for my third study. Here, I use first-principles methods to characterize an atomic-scale BiFeO3-BiMnO3 nanocheckerboard, and find that it has properties that are distinctive from those of either parent compound. More specifically, it has both a spontaneous polarization and magnetization, and also displays a magnetostructural effect. My work on this prototypical multiferroic nanocheckerboard motivates further theoretical and experimental studies of new
Theoretical model study of dynamic ferromagnetic susceptibility in mono-layer graphene
Sahu, Sivabrata; Parashar, S. K. S.; Rout, G. C.
2016-04-01
We report here a microscopic theoretical study of dynamic ferromagnetic spin susceptibility of electrons for graphene systems, which deal with a tight-binding model Hamiltonian consisting of the hopping of electrons up to third-nearest-neighbors, impurity and substrate effects besides Coulomb interaction of electrons at A-and B- sub- lattices. The spin susceptibility involves four two-particle Green's functions, which are calculated by Zubarev's Green's function technique. The up and down electron occupancies at A and B sub-lattices are computed numerically and self-consistently. The temperature dependent susceptibility shows a pronounced peak at Curie temperature for critical Coulomb interaction Uc = 2.2t1.
Microscopic theoretical model study of band gap opening in AA-stacked bi-layer graphene
Sahu, Sivabrata; Parashar, S. K. S.; Rout, G. C.
2016-05-01
We address here a tight-binding theoretical model calculation for AA-stacked bi-layer graphene taking into account of a biased potential between two layers to study the density of states and the band dispersion within the total Brillouin zone. We have calculated the electronic Green's function for electron operator corresponding to A and B sub lattices by Zubarev's Green's function technique from which the electronic density of states and the electron band energy dispersion are calculated. The numerically computed density of states and band energy dispersions are investigated by tuning the biased potential to exhibit the band gap by varying the different physical parameters.
Experimental and Theoretical Studies on Biologically Active Lanthanide (III) Complexes
Kostova, I.; Trendafilova, N.; Georgieva, I.; Rastogi, V. K.; Kiefer, W.
2008-11-01
The complexation ability and the binding mode of the ligand coumarin-3-carboxylic acid (HCCA) to La(III), Ce(III), Nd(III), Sm(III), Gd(III) and Dy(III) lanthanide ions (Ln(III)) are elucidated at experimental and theoretical level. The complexes were characterized using elemental analysis, DTA and TGA data as well as 1H NMR and 13C NMR spectra. FTIR and Raman spectroscopic techniques as well as DFT quantum chemical calculations were used for characterization of the binding mode and the structures of lanthanide(III) complexes of HCCA. The metal—ligand binding mode is predicted through molecular modeling and energy estimation of different Ln—CCA structures using B3LYP/6-31G(d) method combined with a large quasi-relativistic effective core potential for lanthanide ion. The energies obtained predict bidentate coordination of CCA- to Ln(III) ions through the carbonylic oxygen and the carboxylic oxygen. Detailed vibrational analysis of HCCA, CCA- and Ln(III) complexes based on both calculated and experimental frequencies confirms the suggested metal—ligand binding mode. The natural bonding analysis predicts strongly ionic character of the Ln(III)-CCA bonding in the- complexes studied. With the relatively resistant tumor cell line K-562 we obtained very interesting in-vitro results which are in accordance with our previously published data concerning the activity of lanthanide(III) complexes with other coumarin derivatives.
Experimental and Theoretical Studies of Volatile Metal Hydroxides
Myers, Dwight L.; Jacobson, Nathan S.
2015-01-01
Modern superalloys used in the construction of turbomachinery contain a wide range of metals in trace quantities. In addition, metal oxides and silicon dioxide are used to form Thermal Barrier Coatings (TBC) to protect the underlying metal in turbine blades. Formation of volatile hydroxides at elevated temperatures is an important mechanism for corrosion of metal alloys or oxides in combustion environments (N. Jacobson, D. Myers, E. Opila, and E. Copland, J. Phys. Chem. Solids 66, 471-478, 2005). Thermodynamic data is essential to proper design of components of modern gas turbines. It is necessary to first establish the identity of volatile hydroxides formed from the reaction of a given system with high temperature water vapor, and then to determine the equilibrium pressures of the species under operating conditions. Theoretical calculations of reaction energies are an important check of experimental results. This presentation reports results for several important systems: Si-O-H, Cr-O-H, Al-O-H, Ti-O-H, and ongoing studies of Ta-O-H.
A theoretical and spectroscopic study of conformational structures of piroxicam
Souza, Kely Ferreira de; Martins, José A.; Pessine, Francisco B. T.; Custodio, Rogério
2010-02-01
Piroxicam (PRX) has been widely studied in an attempt to elucidate the causes and mechanisms of its side effects, mainly the photo-toxicity. In this paper fluorescence spectra in non-protic solvents and different polarities were carried out along with theoretical calculations. Preliminary potential surfaces of the keto and enol forms were obtained at AM1 level of theory providing the most stable conformers, which had their structure re-optimized through the B3LYP/CEP-31G(d,p) method. From the optimized structures, the electronic spectra were calculated using the TD-DFT method in vacuum and including the solvent effect through the PCM method and a single water molecule near PRX. A new potential surface was constructed to the enol tautomer at DFT level and the most stable conformers were submitted to the QST2 calculations. The experimental data showed that in apolar media, the solution fluorescence is raised. Based on conformational analysis for the two tautomers, keto and enol, the results indicated that the PRX-enol is the main tautomer related to the drug fluorescence, which is reinforced by the spectra results, as well as the interconvertion barrier obtained from the QST2 calculations. The results suggest that the PRX one of the enol conformers presents great possibility of involvement in the photo-toxicity mechanisms.
Theoretical Study of Small (NaI)n Clusters
Aguado, A; López, J M; Alonso, J A
1997-01-01
A systematic theoretical study of stoichiometric clusters (NaI)n up to n=15 is performed using the ab initio Perturbed-Ion (PI) model. The structures obtained are compared to previous pair potential results, and observed differences between (NaI)n clusters and previous ab initio results for other alkali halide clusters are discussed. (NaI)n clusters with n up to 15 do not show yet a marked preference for geometries which are fragments of the bulk lattice. Instead, stacks of hexagonal rings or more open structures are obtained as ground structures in clusters with n=3, 6, 7, 9, 10, 12, 13 and 15, indicating that convergence to bulk structure is not achieved yet at this size range. Low lying isomers which are fragments of the crystal lattice exist, nevertheless, for those cases. The binding energies show that clusters with n=(4), 6, 9 and 12 molecules are specially stable. The binding energy has been decomposed in contributions which allow for an intuitive interpretation. Some electronic properties like ionizat...
Theoretical Study of the Proton Transfer in Enaminones
Directory of Open Access Journals (Sweden)
Rita S. Elias
2012-01-01
Full Text Available Problem statement: Hydrogen bonding has a vital rule to unrevealed the nature of many different interactions both in gas phase and condensed media thus it is one of the most important concepts in chemistry. Enaminoes with their ability to form intrahydrogen bonded cheated rings represent one of the suitable compounds to study such concept. Approach: The three possible tautomers of eneminones were fully optimized at several theoretical levels including B3LYP with the 6-31+G(d,p, 6-311++G(d,p and aug-cc-pVDZ basis sets as well as MP2/6-311++G(d,p level of theory. Then a search for the possible transition state between the two most stable tautomers; the ketamine and the enolimine was done at the B3LYP/6-311++G(d,p level of theory. Results: The ketamine is the most stable while the diketo is the less stable within the tautomeric mixture and the proton transfer occurs through a transition state that is energetically resemble the enolimine tautomer. Conclusion: The interconversion of the tautomers is preferable in the enolimine ketamine direction.
Theoretical study of adsorption of tabun on calcium oxide clusters
Michalkova, A.; Paukku, Y.; Majumdar, D.; Leszczynski, J.
2007-04-01
Interactions of tabun (GA) with non-hydroxylated and hydroxylated CaO clusters have been studied using density functional (DFT) and Møller-Plesset second order perturbation (MP2) levels of theory. The nature of interactions has been further investigated from the topology of charge distribution (using Atoms in Molecules formalism) and molecular electrostatic potential (MEP) surfaces. These adsorption studies indicate that GA adsorbs strongly on the non-hydroxylated CaO cluster through its P dbnd O bond, while interactions of GA on the hydroxylated cluster are weak. These model studies could thus be useful to characterize inorganic oxides for efficient detection and disposal of GA.
Institute of Scientific and Technical Information of China (English)
无
2001-01-01
@@ Genomics is a biology term appeared ten years ago, used to describe the researches of genomic mapping, sequencing, and structure analysis, etc. Genomics, the first journal for publishing papers on genomics research was born in 1986. In the past decade, the concept of genomics has been widely accepted by scientists who are engaging in biology research. Meanwhile, the research scope of genomics has been extended continuously, from simple gene mapping and sequencing to function genomics study. To reflect the change, genomics is divided into two parts now, the structure genomics and the function genomics.
Experimental, theoretical, and numerical studies of small scale combustion
Xu, Bo
Recently, the demand increased for the development of microdevices such as microsatellites, microaerial vehicles, micro reactors, and micro power generators. To meet those demands the biggest challenge is obtaining stable and complete combustion at relatively small scale. To gain a fundamental understanding of small scale combustion in this thesis, thermal and kinetic coupling between the gas phase and the structure at meso and micro scales were theoretically, experimentally, and numerically studied; new stabilization and instability phenomena were identified; and new theories for the dynamic mechanisms of small scale combustion were developed. The reduction of thermal inertia at small scale significantly reduces the response time of the wall and leads to a strong flame-wall coupling and extension of burning limits. Mesoscale flame propagation and extinction in small quartz tubes were theoretically, experimentally and numerically studied. It was found that wall-flame interaction in mesoscale combustion led to two different flame regimes, a heat-loss dominant fast flame regime and a wall-flame coupling slow flame regime. The nonlinear transition between the two flame regimes was strongly dependent on the channel width and flow velocity. It is concluded that the existence of multiple flame regimes is an inherent phenomenon in mesoscale combustion. In addition, all practical combustors have variable channel width in the direction of flame propagation. Quasi-steady and unsteady propagations of methane and propane-air premixed flames in a mesoscale divergent channel were investigated experimentally and theoretically. The emphasis was the impact of variable cross-section area and the flame-wall coupling on the flame transition between different regimes and the onset of flame instability. For the first time, spinning flames were experimentally observed for both lean and rich methane and propane-air mixtures in a broad range of equivalence ratios. An effective Lewis number
Multinucleon short-range correlation model for nuclear spectral functions: Theoretical framework
Artiles, Oswaldo; Sargsian, Misak M.
2016-12-01
We develop a theoretical approach for nuclear spectral functions at high missing momenta and removal energies based on the multinucleon short-range correlation (SRC) model. The approach is based on the effective Feynman diagrammatic method which allows us to account for the relativistic effects important in the SRC domain. In addition to two-nucleon (2N) SRC with center of mass motion we also derive the contribution of three-nucleon SRCs to the nuclear spectral functions. The latter is modeled based on the assumption that 3N SRCs are a product of two sequential short-range nucleon-nucleon (NN) interactions. This approach allows us to express the 3N SRC part of the nuclear spectral function as a convolution of two NN SRCs. Thus the knowledge of 2N SRCs allows us to model both two- and three-nucleon SRC contributions to the spectral function. The derivations of the spectral functions are based on two theoretical frameworks for evaluating covariant Feynman diagrams: In the first, referred to as virtual nucleon approximation, we reduce Feynman diagrams to the time ordered noncovariant diagrams by evaluating nucleon spectators in the SRC at their positive energy poles, neglecting explicitly the contribution from vacuum diagrams. In the second approach, referred to as light-front approximation, we formulate the boost invariant nuclear spectral function in the light-front reference frame in which case the vacuum diagrams are generally suppressed and the bound nucleon is described by its light-front variables such as momentum fraction, transverse momentum, and invariant mass.
Lobach, I.; Benediktovitch, A.
2016-07-01
The possibility of quantitative texture analysis by means of parametric x-ray radiation (PXR) from relativistic electrons with Lorentz factor γ > 50MeV in a polycrystal is considered theoretically. In the case of rather smooth orientation distribution function (ODF) and large detector (θD >> 1/γ) the universal relation between ODF and intensity distribution is presented. It is shown that if ODF is independent on one from Euler angles, then the texture is fully determined by angular intensity distribution. Application of the method to the simulated data shows the stability of the proposed algorithm.
Indian Academy of Sciences (India)
Sambath Baskaran; Perumal Balu; Chinnappan Sivasankar
2015-01-01
Atmospheric N2 can be cleaved directly to yield metal-nitride (before proceeding to the functionalization of N of coordinated N2) and subsequently functionalized to ammonia using M(III)(NMe2)3 (M = W/Mo) as a catalyst, and suitable proton and electron sources. The calculated energies of thermodynamic and kinetic states of the various intermediates and transition states in the reaction coordinate to yield ammonia confirmed the viability of the proposed reaction pathway. Rationale of different pathways have been examined and discussed in detail. Changes in the structural features of the catalyst and some important intermediates and transition states have also been examined.
Theoretical study of the unimolecular dissociation of HCO
Whittier, Gregory Scott
This thesis offers a detailed theoretical study of the unimolecular dissociation of formyl radical, HCO, which is an important intermediate in combustion chemistry. A quantum mechanical treatment of the dissociation of isolated HCO is presented along with a mixed quantum/classical study of the excitation and deexcitation of HCO in collisions of HCO with the bath gas Ar. The results are then used to model the kinetics of the collision-induced dissociation of HCO by Ar. Resonance states of HCO are calculated for total angular momentum J = 0, 1, and 3 using the artificial boundary inhomogeneity (ABI) method of Jang and Light [J. Chem. Phys. 102, 3262 (1995)]. Resonance energies and widths are determined by analyzing the Smith lifetime matrix. A resonance search algorithm and a method for resolving overlapping resonances are described. The accurate prediction of J = 3 resonances from J = 0 and 1 data is tested with good results for excited stretch resonance and less accurate results for bending resonances, demonstrating the degree of separability of vibration from overall rotation for these quasi-bound states. A quantum/classical time-dependent self-consistent field (Q/C TDSCF) approach is used to simulate the dynamics of collisions of Ar with HCO. State-to-state cross sections and thermal rate constants for vibrational transitions are presented. Using this model together with assumptions about the rotational energy transfer and a master equation treatment of the kinetics, the low-pressure thermal rate of collision-induced dissociation was calculated over the 300-4000 K temperature range. Comparison with experiment shows good agreement at high temperatures and poor agreement at low temperatures. The high temperature results were sufficient to obtain an Arrhenius expression for the rate that agrees with all experimental results of which we are aware.
Density functional theory studies of etoricoxib
Sachdeva, Ritika; Kaur, Prabhjot; Singh, V. P.; Saini, G. S. S.
2016-05-01
Etoricoxib is a COX-2 selective inhibitor drug with molecular formula C18H15ClN2O2S. It is primarily used for the treatment of arthritis(rheumatoid, psoriatic, osteoarthritis), ankylosing spondylitis, gout and chronic low back pain. Theoretical studies of the molecule including geometry optimization and vibrational frequency calculations were carried out with the help of density functional theory calculations using 6-311++ g (d, p) basis set and B3LYP functional.
Theoretical studies on the reaction pathways of electronically excited DAAF
Energy Technology Data Exchange (ETDEWEB)
Quenneville, Jason M [Los Alamos National Laboratory; Moore, David S [Los Alamos National Laboratory
2009-01-01
The use of temporally and spectrally shaped ultrafast laser pulses to initiate, as well as detect, high explosives is being explored at Los Alamos. High level ab initio calculations, presented here, are employed to help guide and interpret the experiments. The ground and first excited electronic states of 3,3{prime}-diamino-4,4{prime}-azoxyfurazan (DAAF) are investigated using complete active space self-consistent field (CASSCF) and time-dependent density functional theory (TD-DFT). The geometrical and energetic character of the excited state minima, conical intersections and reaction pathways of DAAF are described. Two radiative and two non-radiative excited state population quenching mechanisms are outlined, and possible pathways for photochemical and spectroscopic control are discussed. The use of laser light to control chemical reactions has many applications. The initiation and the detection of explosives are two such applications currently under development at Los Alamos. Though inherently experimental, the project can be aided by theory through both prediction and interpretation. When the laser light is in the UV/visible region of the electromagnetic spectrum, the absorbing molecule is excited electronically and excitation decay may occur either radiatively (fluorescence or phosphorescence) or non-radiatively (through internal conversion). In many cases decay of the excitation occurs through a mixture of processes, and maximizing the desired result requires sophisticated laser pulses whose amplitude has been optimally modulated in time and/or frequency space. Control of cis-stilbene photochemistry was recently demonstrated in our group, and we aim to extend this work to high explosive compounds. Maximizing radiative decay leads to increased fluorescence quantum yields and enhances the possibility of spectral detection of the absorbing molecule. Maximizing non-radiative decay can lead to chemistry, heating of the sample and possibly detonation initiation in
Lara, O
1995-01-01
continued fractions are now in progress. It is well known that multichannel effects strongly influence the low-energy electron scattering by atoms and molecules. Nevertheless, the inclusion of such effects on the calculations of scattering cross sections remains a considerable task for the area researches due to the complexity of the problem. In the present study we aim to develop a new theoretical method which can be efficiently applied to the multichannel scattering studies. Two new theoretical formalisms namely the Multichannel sup - C-Functional Method have been proposed. Both methods were developed on the base of well-known distorted-wave method combined with Schwinger variational principle. In addition, an integrative method proposed by Horacek and Sasakawa in 1983, the method of continued fractions is adapted by the first time to multichannel scatterings. Numerical test of these three methods were carried out through applications to solve the multichannel scattering problems involving the interaction o...
The theoretical studies of piezoresistive effect in diamond films
Institute of Scientific and Technical Information of China (English)
无
2002-01-01
Based on the Fuchs and Sondheimer thin film theory (F-S film theory) and a revised valence band split-off model, considering a mixed scattering by lattice vibrations, ionized impurities and surfaces, a theoretical description of the piezoresistive effect (PR effect) in p-type heteroepitaxial diamond films was presented by solving the Boltzmann transport equation in the relaxation time approximation and using the parallel connection resistance model. A calculating expression of the PR effect was given. The main characteristics that were identical with the experiment were obtained by theoretical calculation. Giving out a model to show that the energy level interval between the split-off band and the heavy-hole band was changed by strain, a reasonable explanation was presented for the error between experimental results and theoretical values of saturated PR effect under big strain.
Theoretical Study of the Compound Parabolic Trough Solar Collector
Directory of Open Access Journals (Sweden)
Dr. Subhi S. Mahammed
2012-06-01
Full Text Available Theoretical design of compound parabolic trough solar collector (CPC without tracking is presented in this work. The thermal efficiency is obtained by using FORTRAN 90 program. The thermal efficiency is between (60-67% at mass flow rate between (0.02-0.03 kg/s at concentration ratio of (3.8 without need to tracking system.The total and diffused radiation is calculated for Tikrit city by using theoretical equations. Good agreement between present work and the previous work.
Study of cognitive sphere in children and adolescents with congenital myopathy (theoretical review
Directory of Open Access Journals (Sweden)
V. A. Erokhina
2013-08-01
Full Text Available This paper presents an analysis of current approaches to the study of states of higher mental functions in children and adolescents suffering from various forms of hereditary myopathies. The aim of this work is to study the theoretical rationale and the possibility of specific disorders of mental function in children and adolescents with congenital myopathies. To achieve this objective during the study it was necessary to solve the following problems: give a description of the various groups and forms of congenital myopathies, their clinical characteristics; justify the possibility of considering the hereditary myopathies as a factor in the formation of changes in visual-spatial activities and thinking; evaluate the possibility to use complex neuropsychological psycho-diagnostic techniques for investigating the state of the higher mental functions of children with congenital myopathies. The possibility of neuropsychological correction for this category of patients is discussed also.
Theoretical and experimental NMR studies on muscimol from fly agaric mushroom (Amanita muscaria)
Kupka, Teobald; Wieczorek, Piotr P.
2016-01-01
In this article we report results of combined theoretical and experimental NMR studies on muscimol, the bioactive alkaloid from fly agaric mushroom (Amanita muscaria). The assignment of 1H and 13C NMR spectra of muscimol in DMSO-d6 was supported by additional two-dimensional heteronuclear correlated spectra (2D NMR) and gauge independent atomic orbital (GIAO) NMR calculations using density functional theory (DFT). The effect of solvent in theoretical calculations was included via polarized continuum model (PCM) and the hybrid three-parameter B3LYP density functional in combination with 6-311++G(3df,2pd) basis set enabled calculation of reliable structures of non-ionized (neutral) molecule and its NH and zwitterionic forms in the gas phase, chloroform, DMSO and water. GIAO NMR calculations, using equilibrium and rovibrationally averaged geometry, at B3LYP/6-31G* and B3LYP/aug-cc-pVTZ-J levels of theory provided muscimol nuclear magnetic shieldings. The theoretical proton and carbon chemical shifts were critically compared with experimental NMR spectra measured in DMSO. Our results provide useful information on its structure in solution. We believe that such data could improve the understanding of basic features of muscimol at atomistic level and provide another tool in studies related to GABA analogs.
Directory of Open Access Journals (Sweden)
Wi Hoon eJung
2013-10-01
Full Text Available One major characteristic of experts is intuitive judgment, which is an automatic process whereby patterns stored in memory through long-term training are recognized. Indeed, long-term training may influence brain structure and function. A recent study revealed that chess experts at rest showed differences in structure and functional connectivity (FC in the head of caudate, which is associated with rapid best next-move generation. However, less is known about the structure and function of the brains of Baduk experts compared with those of experts in other strategy games. Therefore, we performed voxel-based morphometry and FC analyses in Baduk experts to investigate structural brain differences and to clarify the influence of these differences on functional interactions. We also conducted graph theoretical analysis to explore the topological organization of whole-brain functional networks. Compared to novices, Baduk experts exhibited decreased and increased gray matter volume in the amygdala and nucleus accumbens, respectively. We also found increased FC between the amygdala and medial orbitofrontal cortex and decreased FC between the nucleus accumbens and medial prefrontal cortex. Further graph theoretical analysis revealed differences in measures of the integration of the network and in the regional nodal characteristics of various brain regions activated during Baduk. This study provides evidence for structural and functional differences as well as altered topological organization of the whole-brain functional networks in Baduk experts. Our findings also offer novel suggestions about the cognitive mechanisms behind Baduk expertise, which involves intuitive decision-making mediated by somatic marker circuitry and visuospatial processing.
Examining the outsourcing of information systems functions from diverse theoretical perspectives
Moura, Isabel Cristina A. A.; Grover, Varun
2001-01-01
Submitted to "Information & Management" in 2001. In recent years there has been a significant increase in the incidence of information systems (IS) outsourcing. Technological uncertainty, cost reduction, the need to concentration on core business, and the increasing quality and competition among a growing cadre of service providers, (e.g.) are often discussed as key outsourcing motivators. While a number of theoretical frameworks have been used to structure studies on this phenomenon, the ...
THEORETICAL STUDY (AB INITIO AND DFT METHODS) ON ...
African Journals Online (AJOL)
3Division of Computational Physics, Institute for Computational Science, Ton ... 4Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, ... a complex of Al(III) with xylenol orange as an ultra-sensitive colored reagent ..... Husain, A. Pharmaceutical Analysis, Theoretical Basis of Analysis: Complexometric.
A theoretical study of Favorskii reaction stereochemistry. Lessons in torquoselectivity.
Hamblin, Graham D; Jimenez, Raphael P; Sorensen, Ted S
2007-10-12
The mechanisms of the chloroenolate-->cyclopropanone step of the "normal" Favorskii rearrangement have been investigated in detail using high-level ab initio calculations. A series of simple alpha-chloroenolates, based on chloroacetone (6), all monomethyl derivatives (7-9), a dimethyl analogue (10), and 1-acetyl-1-chlorocyclohexane (11) was first used to explore and define the basic features of the mechanism, which include the finding of both an "inversion" and a "retention" transition state and that in most cases these arise from separate ground-state conformations of the chloroenolate. These theoretical studies were then extended to an isomeric pair of chloroenolates 1 and 2, the cis- and trans-2-methyl derivatives of 11, which are the reactive intermediates involved in a well-known experimental study carried out by Stork and Borowitz (S-B). Finally, three alpha-chlorocyclohexanone enolate systems 12-14 were studied, since these intermediates have a more restricted enolate geometry. The "inversion" mechanism has been described as an SN2 process but the present results, while supporting a concerted process, is better described as an oxyallyl structure undergoing concerted ring closure. The "retention" mechanism has been described as SN1-like, but the calculations show that this process is also concerted, although much less so, and again involves oxyallyl-like transition-states. The model systems 6-8, 10, and 11 with a potential plane of symmetry have two enantiomeric transition states for inversion and another two for retention of configuration (at the C-Cl center). With 9 and the S-B models 1 and 2, with no symmetry plane, there are a calculated total of four diastereomeric transition states for cyclopropanone ring closure in each case, two for inversion and two for retention. While the transition-state energies calculated for simple chloroenolates favor the inversion process, the S-B models 1 and 2 have almost equal inversion-retention transition-state energies
Theoretical Study on Catalyst Activation of Palladacycles in Heck Reaction
Institute of Scientific and Technical Information of China (English)
WANG Chen; FU Yao; LI Zhe; GUO Qing-Xiang
2008-01-01
A computational study with the B3PW91 density functional theory was carried out on the activation process of palladacycles as catalysts in the Heck reaction.Two possible pathways (i.e.anion reductive cleavage of the Pd-C bond,and olefin insertion into the Pd-C bond followed by β-H elimination)were taken into consideration.Computational results indicate that the palladacycles are activated via olefin insertion into the Pd-C bond followed by β-H elimination in the reaction conditions.
A theoretical study on interaction of proline with gold cluster
Indian Academy of Sciences (India)
Sandhya Rai; N V Suresh Kumar; Harjinder Singh
2012-06-01
Interaction of proline with gold cluster was studied using density functional theory (DFT). Two types of mixed basis sets UB3LYP/6-311++G ∪ LANL2MB and UB3LYP/6-311++G ∪ LANL2DZ were used for optimization of complex structures. Proline interacts with gold cluster either through one anchor bond, N–Au or an anchor bond O–Au associated with a non-conventional O–H…Au hydrogen bond. Among these interactions, higher tendency for interaction is seen with Au cluster through amide terminal. Natural bond orbital analysis (NBO) is used to substantiate the results.
Pan, Yi; Lau, Kai-Chung; Al-Mogren, Muneerah Mogren; Mahjoub, Ahmed; Hochlaf, Majdi
2014-10-01
We treat theoretically 2-quinolinol(lactam), an analog of carbostyril and DNA bases. We characterized the ground state structure of 2-quinolinol and its isomer(lactim) using density functional theory(DFT). The reaction profile and energetics for lactam-lactim tautomerization and cis-lactim to trans-lactim isomerization predicted with explicitly correlated methods. We explored the pattern of the lowest singlet and triplet manifolds of states and electronic S1 ← S0 transitions using multiconfigurational methodologies. The theoretical results are compared with available experimental data and used to interpret the on-going photoelectron study of 2-quinolinol. Our analysis should help to understand the effect of tautomerism and aromaticity on the DNA bases.
Using Defects in Materials to Store Energy: a Theoretical Study
Lu, I.-Te; Bernardi, Marco
We study the energy stored by defects in materials using density functional theory (DFT) calculations. Leveraging experimental data to estimate the energy density of defects, expressed as the defect formation energy per unit volume (units of MJ/L) or weight (units of MJ/kg), we identify candidates for high energy density storage, including tungsten, diamond, graphite, silicon, and graphene. DFT calculations are applied to these materials to study the formation energy of vacancies, interstitials, and Frenkel pairs. Our results indicate that the energy density stored by defects in these materials, with experimentally accessible non-equilibrium defect concentrations, can be higher than that of common energy storage technologies such as lithium batteries and supercapacitors. We discuss storage of solar energy and electrical energy (through ion bombardment) using defects.
The physics of neutrino cross sections: theoretical studies
Alvarez-Ruso, Luis
2016-01-01
The present status of neutrino cross section physics is reviewed focusing on the recent theoretical developments in quasielastic scattering, multi-nucleon contributions to the inclusive scattering and pion production on nucleons and nuclei. A good understanding of these processes is crucial to meet the precision needs of neutrino oscillation experiments. Some of the challenges that arise in the consistent description of MiniBooNE and MINERvA recent data are discussed.
Theoretical Study of Electronic Properties of Carbon Allotropes
Dral, Pavlo
2013-01-01
This doctoral thesis describes theoretical investigations of the different physicochemical and above all electronic properties of numerous already discovered and yet to be synthesized modern carbon allotropes, their model compounds and derivatives. In the last century it was ascertained that carbon is not only the most important chemical element for the existence of living beings, but is also becoming increasingly more important for electronics and especially in recent decades for molecula...
Theoretical study of a melting curve for tin
Institute of Scientific and Technical Information of China (English)
Xi Feng; Cai Ling-Cang
2009-01-01
The melting curve of Sn has been calculated using the dislocation-mediated melting model with the 'zone-linking method'. The results are in good agreement with the experimental data. According to our calculation, the melting temperature of γ-Sn at zero pressure is about 436 K obtained by the extrapolation of the method from the triple point of Sn. The results show that this calculation method is better than other theoretical methods for predicting the meltingcurve of polymorphic material Sn.
[Theoretical studies in weak, electromagnetic and strong interactions. Attachments
Energy Technology Data Exchange (ETDEWEB)
Nandi, S.
1999-09-01
The project covered a wide area of current research in theoretical high-energy physics. This included Standard Model (SM) as well as physics beyond the Standard Model. Specific topics included supersymmetry (SUSY), perturbative quantum chromodynamics (QCD), a new weak interaction for the third family (called topflavor), neutrino masses and mixings, topcolor model, Pade approximation, and its application to perturbative QCD and other physical processes.
Theoretical Study of First Language Transfer in Second Language Learning
Institute of Scientific and Technical Information of China (English)
邱达希
2015-01-01
The role and impact offirst language knowledge and how it affects Chinese learners' learning process are significant issues in second language learning.In discussing the role of first language transfer in second language learning,the theoretical understanding of first language transfer will be considered.The next section will go into further detail in the implications and suggestions for teaching and learning English writing and finally conclusions will be drawn from the reading and discussions within this paper.
Theoretical Study of First Language Transfer in Second Language Learning
Institute of Scientific and Technical Information of China (English)
邱达希
2015-01-01
The role and impact of first language knowledge and how it affects Chinese learners’ learning process are significant issues in second language learning.In discussing the role of first language transfer in second language learning,the theoretical understanding of first language transfer will be considered.The next section will go into further detail in the implications and suggestions for teaching and learning English writing and finally conclusions will be drawn from the reading and discussions within this paper.
Theoretical study on the flow about Savonius rotor
Ogawa, T.
1984-03-01
A method for the two-dimensional analysis of the separated flow about Savonius rotors is presented. Calculations are performed by combining the singularity method and the discrete vortex method. The method is applied to the simulation of flows about a stationary rotor and a rotating rotor. Moreover, torque and power coefficients are computed and compared with the experimental results presented by Sheldahl et al. Theoretical and experimental results agree well qualitatively.
Intrinsic functional brain architecture derived from graph theoretical analysis in the human fetus.
Directory of Open Access Journals (Sweden)
Moriah E Thomason
Full Text Available The human brain undergoes dramatic maturational changes during late stages of fetal and early postnatal life. The importance of this period to the establishment of healthy neural connectivity is apparent in the high incidence of neural injury in preterm infants, in whom untimely exposure to ex-uterine factors interrupts neural connectivity. Though the relevance of this period to human neuroscience is apparent, little is known about functional neural networks in human fetal life. Here, we apply graph theoretical analysis to examine human fetal brain connectivity. Utilizing resting state functional magnetic resonance imaging (fMRI data from 33 healthy human fetuses, 19 to 39 weeks gestational age (GA, our analyses reveal that the human fetal brain has modular organization and modules overlap functional systems observed postnatally. Age-related differences between younger (GA <31 weeks and older (GA≥31 weeks fetuses demonstrate that brain modularity decreases, and connectivity of the posterior cingulate to other brain networks becomes more negative, with advancing GA. By mimicking functional principles observed postnatally, these results support early emerging capacity for information processing in the human fetal brain. Current technical limitations, as well as the potential for fetal fMRI to one day produce major discoveries about fetal origins or antecedents of neural injury or disease are discussed.
Intrinsic functional brain architecture derived from graph theoretical analysis in the human fetus.
Thomason, Moriah E; Brown, Jesse A; Dassanayake, Maya T; Shastri, Rupal; Marusak, Hilary A; Hernandez-Andrade, Edgar; Yeo, Lami; Mody, Swati; Berman, Susan; Hassan, Sonia S; Romero, Roberto
2014-01-01
The human brain undergoes dramatic maturational changes during late stages of fetal and early postnatal life. The importance of this period to the establishment of healthy neural connectivity is apparent in the high incidence of neural injury in preterm infants, in whom untimely exposure to ex-uterine factors interrupts neural connectivity. Though the relevance of this period to human neuroscience is apparent, little is known about functional neural networks in human fetal life. Here, we apply graph theoretical analysis to examine human fetal brain connectivity. Utilizing resting state functional magnetic resonance imaging (fMRI) data from 33 healthy human fetuses, 19 to 39 weeks gestational age (GA), our analyses reveal that the human fetal brain has modular organization and modules overlap functional systems observed postnatally. Age-related differences between younger (GA brain modularity decreases, and connectivity of the posterior cingulate to other brain networks becomes more negative, with advancing GA. By mimicking functional principles observed postnatally, these results support early emerging capacity for information processing in the human fetal brain. Current technical limitations, as well as the potential for fetal fMRI to one day produce major discoveries about fetal origins or antecedents of neural injury or disease are discussed.
Theoretical Study of Ion Transport in the Gramicidin a Channel
Roux, Benoi T.
Modern techniques are used to study the permeation process of ions through the gramicidin A channel. The conformation of the gramicidin molecule is investigated experimentally in dimethylsulfoxide/acetone using the techniques of two-dimensional NMR spectroscopy. An empirical energy function is developed from ab initio calculations to represent the interaction of Li^{+}, Na^{+} and K^ {+} ions with the backbone of polypeptides; the parameters are tested in dense systems with free energy simulations. The dynamics of the gramicidin A channel dimer in the absence of water and ions is studied in the harmonic approximation by a vibrational analysis of the atomic motions relative to their equilibrium positions. The behavior of the water molecules in the channel is studied with a molecular dynamics simulation of a fully solvated Gramicidin A dimer embedded in a model membrane. the potential of mean force and the mobility of Na^{+ }, K^{+} and water are calculated in the interior of a gramicidin-like periodic poly (L,D)-alanine beta -helix. The potential of mean force of Na^ {+} ion along the axis of the gramicidin A channel is calculated with a molecular dynamics simulation of a fully solvated Gramicidin A dimer embedded in a model membrane; the gramicidin channel is modeled as a right -handed head-to-head beta-helix dimer. Binding sites are found at the extremities of the channel; no large activation energy barrier is caused by the dehydration process at the entrance of the channel. In the appendices, Statistical Mechanical theories are used to investigate the equilibrium and dynamical properties of the liquid state. A theory of aqueous solutions is used to provide an interpretation for the Born model of ion hydration at the molecular level; the Born radius of hydration is interpreted in terms of the first peak in the solute-solvent radial distribution function. We show that some proposed closures for the RISM equation of Chandler and Andersen possess no solution because
Hydrogen motion in proton sponge cations: a theoretical study.
Horbatenko, Yevhen; Vyboishchikov, Sergei F
2011-04-18
This work presents a study of intramolecular NHN hydrogen bonds in cations of the following proton sponges: 2,7-bis(trimethylsilyl)-1,8-bis(dimethylamino)naphthalene (1), 1,6-diazabicyclo[4.4.4.]tetradecane (2), 1,9-bis(dimethylamino)dibenzoselenophene (3), 1,9-bis(dimethylamino)dibenzothiophene (4), 4,5-bis(dimethylamino)fluorene (5), quino[7,8-h]quinoline (6) 1,2-bis(dimethylamino)benzene (7), and 1,12-bis(dimethylamino)benzo[c]phenantrene (8). Three different patterns were found for proton motion: systems with a single-well potential (cations 1-2), systems with a double-well potential and low proton transfer barrier, ΔEe (cations 3-5), and those with a double-well potential and a high barrier (cations 6-8). Tests of several density functionals indicate that the PBEPBE functional reproduces the potential-energy surface (PES) obtained at the MP2 level well, whereas the B3LYP, MPWB1K, and MPW1B95 functionals overestimate the barrier. Three-dimensional PESs were constructed and the vibrational Schrödinger equation was solved for selected cases of cation 1 (with a single-well potential), cation 4 (with a ΔEe value of 0.1 kcal mol(-1) at the MP2 level), and cations 6 (ΔEe = 2.4 kcal mol(-1)) and 7 (ΔEe=3.4 kcal mol(-1)). The PES is highly anharmonic in all of these cases. The analysis of the three-dimensional ground-state vibrational wave function shows that the proton is delocalized in cations 1 and 4, but is rather localized around the energy minima for cation 7. Cation 6 is an intermediate case, with two weakly pronounced maxima and substantial tunneling. This allows for classification of proton sponge cations into those with localized and those with delocalized proton behavior, with the borderline between them at ΔEe values of about 1.5 kcal mol(-1). The excited vibrational states of proton sponge cations with a low barrier can be described within the framework of a simple particle-in-a-box model. Each cation can be assigned an effective box width.
Study of nonplanarity of peptide bond using theoretical calculations.
Selvarengan, P; Kolandaivel, P
2005-08-01
The conformational dependence of nonplanarity of the peptide bond of formylglycinamide has been studied using ab initio and density functional theory methods. Hartree-Fock self-consistent field theory (HF), Møller-Plesset perturbation theory (MP2) of ab initio and B3LYP level of theory of dft method have been used employing 6-31++G** basis set. The MP2 method predicts better results than HF and B3LYP levels of theory for conformational stability dependence of nonplanarity. Systematic dependence of planarity deviation has been observed in MP2 theory. The chemical hardness values successfully predict the conformational region, but fail to obey maximum hardness principle. It is concluded that the most reliable dft method could not successfully predict the planarity of peptide bond in comparison with electron correlated method of ab initio method.
Hydroxyl radical induced transformation of phenylurea herbicides: A theoretical study
Mile, Viktória; Harsányi, Ildikó; Kovács, Krisztina; Földes, Tamás; Takács, Erzsébet; Wojnárovits, László
2017-03-01
Aromatic ring hydroxylation reactions occurring during radiolysis of aqueous solutions are studied on the example of phenylurea herbicides by Density Functional Theory calculations. The effect of the aqueous media is taken into account by using the Solvation Model Based on Density model. Hydroxyl radical adds to the ring because the activation free energies (0.4-47.2 kJ mol-1) are low and also the Gibbs free energies have high negative values ((-27.4) to (-5.9) kJ mol-1). According to the calculations in most of cases the ortho- and para-addition is preferred in agreement with the experimental results. In these reactions hydroxycyclohexadienyl type radicals form. In a second type reaction, when loss of chlorine atom takes place, OH/Cl substitution occurs without cyclohexadienyl type intermediate.
Homogenisation of linear electromagnetic materials. Theoretical and numerical studies
MacKay, T G
2001-01-01
of the real and imaginary parts of the constitutive dyadics do not coincide, is demonstrated. Additionally, orthorhombic biaxial structures are presented which can arise even though the distinguished axes of the component phases are non-orthogonal. Secondly, the strong-property-fluctuation theory (SPFT) is developed for bianisotropic materials, under the bilocal approximation. The SPFT represents a major advance over traditional approaches to homogenisation, such as provided by the Maxwell Garnett and Bruggeman formalisms, by accommodating a more comprehensive description of the distributional statistics of the component phases. In particular, the SPFT takes account of scattering losses and in its zero-order implementation the SPFT reduces to the Bruggeman homogenisation formalism. Detailed numerical studies are presented which highlight the role of the correlation length, as well as the component phase topology and orientation diversity. Also, the choice of covariance function is demonstrated to exert only a...
Claret, A.
2016-04-01
Aims: Recent observations of very fast rotating stars show systematic deviations from the von Zeipel theorem and pose a challenge to the theory of gravity-darkening exponents (β1). In this paper, we present a new insight into the problem of temperature distribution over distorted stellar surfaces to try to reduce these discrepancies. Methods: We use a variant of the numerical method based on the triangles strategy, which we previously introduced, to evaluate the gravity-darkening exponents. The novelty of the present method is that the theoretical β1 is now computed as a function of the optical depth, that is, β1 ≡ β1(τ). The stellar evolutionary models, which are necessary to obtain the physical conditions of the stellar envelopes/atmospheres inherent to the numerical method, are computed via the code GRANADA. Results: When the resulting theoretical β1(τ) are compared with the best accurate data of very fast rotators, a good agreement for the six systems is simultaneously achieved. In addition, we derive an equation that relates the locus of constant convective efficiency in the Hertzsprung-Russell (HR) diagram with gravity-darkening exponents.
Directory of Open Access Journals (Sweden)
Mariia Rubtcova
2016-05-01
Full Text Available The paper aims at examining possibilities and limits of Systemic functional linguistics theoretical framework. Ideologically SFL concept was associated with the ideas of social justice and equality, the building of the society of equal opportunities through the educational system. The most interesting ideas arose when the SFL representatives thought about the development of English as a native language and were connected with the overcoming of class distinctions. The current version - genre-based approach – has serious limits. The desire of a genre-based approach to the systematization of genres carries a risk of cultural contradictions and conflict of cultures. However, the basic theoretical SFL principles are still in the stage of formation, as SFL researchers seek to avoid some rigidity of the classical institutional (genre approach, which is in contradiction with the principles of diversity. The founder M. Halliday offered ideas for the organization of a flexible approach based on International English that may become World Englishes, developing in order to adapt to the meanings of other cultures. Therefore, an SFL approach still needs some alterations to spread outside the Western world and conform to the new culture for it. Besides, we can think about proposals of Halliday’s supporters to develop the own version of English for non-Western countries, considering its culture and mentality.
Ogle, K.; Fell, M.; Barber, J. J.
2016-12-01
Empirical, field studies of plant functional traits have revealed important trade-offs among pairs or triplets of traits, such as the leaf (LES) and wood (WES) economics spectra. Trade-offs include correlations between leaf longevity (LL) vs specific leaf area (SLA), LL vs mass-specific leaf respiration rate (RmL), SLA vs RmL, and resistance to breakage vs wood density. Ordination analyses (e.g., PCA) show groupings of traits that tend to align with different life-history strategies or taxonomic groups. It is unclear, however, what underlies such trade-offs and emergent spectra. Do they arise from inherent physiological constraints on growth, or are they more reflective of environmental filtering? The relative importance of these mechanisms has implications for predicting biogeochemical cycling, which is influenced by trait distributions of the plant community. We address this question using an individual-based model of tree growth (ACGCA) to quantify the theoretical trait space of trees that emerges from physiological constraints. ACGCA's inputs include 32 physiological, anatomical, and allometric traits, many of which are related to the LES and WES. We fit ACGCA to 1.6 million USFS FIA observations of tree diameters and heights to obtain vectors of trait values that produce realistic growth, and we explored the structure of this trait space. No notable correlations emerged among the 496 trait pairs, but stepwise regressions revealed complicated multi-variate structure: e.g., relationships between pairs of traits (e.g., RmL and SLA) are governed by other traits (e.g., LL, radiation-use efficiency [RUE]). We also simulated growth under various canopy gap scenarios that impose varying degrees of environmental filtering to explore the multi-dimensional trait space (hypervolume) of trees that died vs survived. The centroid and volume of the hypervolumes differed among dead and live trees, especially under gap conditions leading to low mortality. Traits most predictive
Theoretical studies of permeability inversion from seismoelectric logs
Hu, H.; Guan, W.; Zhao, W.
2012-04-01
Permeability is one of the most important parameters for evaluating the level of difficulty in oil and gas exploitation. A quick, continuous and accurate in-situ estimate of reservoir permeability is highly significant. Stoneley wave logs have been used to determine formation permeability (Tang and Cheng, 1996). However, the inversion errors of this method are too big in low-permeability formations, especially in high-porosity and low-permeability formations resulting from the high clay content in pores. In this study, we propose to invert permeability by using the full waveforms of seismoelectric logs with low frequencies. This method is based on the relationship of permeability with the ratio of the electric excitation intensity to the pressure field's (REP) with respect to the Stoneley wave in seismoelectric logs. By solving the governing equations for electrokinetic coupled wavefields in homogeneous fluid-saturated porous media (Pride, 1994), we calculate the full waveforms of the borehole seismoelectric wavefields excited by a point pressure source and investigate frequency-dependent excitation intensities of the mode waves and excitation intensities of the real branch points in seismoelectric logs. It is found that the REP's phase, which reflects the phase discrepancy between the Stoneley-wave-induced electric field and the acoustic pressure, is sensitive to formation permeability. To check the relation between permeability and REP's phase qualitatively, an approximate expression of the tangent of the REP's argument is derived theoretically as tan(θEP) ≈-ωc/ω = -φη/ (2πfα ∞ρfκ0), where θEPdenotes the arguments of the REP and their principal value is the REP's phase,ω is the angular frequency,ωc is a critical angular frequency that separates the low-frequency viscous flow from the high-frequency inertial flow, φ is the porosity, α∞ is the tortuosity, κ0 is the Darcy permeability, ρf and η are the density and the viscosity of the pore
Theoretical studies on the photoionization cross-sections of solid silver
Institute of Scientific and Technical Information of China (English)
Ma Xiao-Guang; Sun Wei-Guo
2005-01-01
An alternative expression for photoionization cross-section of atoms or molecules and a dielectric influence function (DIF) in a high-density system proposed recently are used to study the photoionization cross-sections of solid silver. It is suggested that a density turning point (DTP) of a photoionized system may be viewed as the critical point where the photoionization properties of atoms in a real system may have a notable change. The results show that the present theoretical photoionization cross-sections are in good agreement with the experimental results of a silver crystal both in structure and in magnitude.
Synthesis, conformational and theoretical studies of 1,n-di(2-formyl-4-phenylazophenoxy)alkanes
Balachander, R.; Manimekalai, A.
2016-01-01
1,n-di(2-Formyl-4-phenylazophenoxy)alkanes 1 and 2 and 1,3-di(2-formyl-4-phenylazophenoxymethyl)benzene 3 were synthesis and characterized by FT-IR, UV-Vis, 1H, 13C NMR and mass spectral studies. The stable conformations of 1-3 were predicted theoretically and selected geometrical parameters were derived from optimized structures. The molecular parameters of HOMO-LUMO energies, polarizability, hyperpolarizability, natural bond orbital (NBO), atom in molecule (AIM) analysis and molecular electrostatic potential (MEP) surfaces were determined by the density functional theory (DFT) method and analysed.
Schiller, Jana; Pérez-Ruiz, Raúl; Sampedro, Diego; Marqués-López, Eugenia; Herrera, Raquel P.; Díaz Díaz, David
2016-01-01
In this work we demonstrate the ability of a multifaceted N,N′-disubstituted urea to selectively recognize fluoride anion (F−) among other halides. This additional function is now added to its already reported organocatalytic and organogelator properties. The signaling mechanism relies on the formation of a charge-transfer (CT) complex between the urea-based sensor and F¯ in the ground state with a high association constant as demonstrated by absorption and fluorescence spectroscopy. The nature of the hydrogen bonding interaction between the sensor and F¯ was established by 1H-NMR studies and theoretical calculations. Moreover, the recovery of the sensor was achieved by addition of methanol. PMID:27171087
Gas adsorption on graphene doped with B, N, Al, and S: A theoretical study
Dai, Jiayu; Yuan, Jianmin; Giannozzi, Paolo
2009-12-01
The adsorption of several common gas molecules over boron-, nitrogen-, aluminum-, and sulfur-doped graphene was theoretically studied using density-functional theory. B- and N-doped graphene retain a planar form, while Al and S atoms protrude out of the graphene layer. We find that only NO and NO2 bind to B-doped graphene, while only NO2 binds to S-doped graphene. Al-doped graphene is much more reactive and binds many more gases, including O2. We suggest that B- and S-doped graphene could be a good sensor for polluting gases such as NO and NO2.
Energy Technology Data Exchange (ETDEWEB)
Gece, Goekhan, E-mail: gokhangc@gmail.co [Department of Physical Chemistry, Faculty of Science, Ankara University, Besevler, 06100 Ankara (Turkey); Bilgic, Semra [Department of Physical Chemistry, Faculty of Science, Ankara University, Besevler, 06100 Ankara (Turkey)
2010-10-15
To clarify the inhibition efficiencies of a total of 12 amino acids for the corrosion of nickel in acidic medium, a density functional theory (DFT) study was carried out using the B3LYP/LANL2DZ method. Quantum chemical descriptors such as the energy of highest occupied molecular orbital (E{sub HOMO}), energy of lowest unoccupied molecular orbital (E{sub LUMO}), and the energy gap ({Delta}E) were calculated. Equations were proposed using linear regression analysis to determine the most effective parameter on inhibition efficiency. The theoretically obtained results were found to be consistent with the experimental data reported.
Schiller, Jana; Pérez-Ruiz, Raúl; Sampedro, Diego; Marqués-López, Eugenia; Herrera, Raquel P; Díaz Díaz, David
2016-05-09
In this work we demonstrate the ability of a multifaceted N,N'-disubstituted urea to selectively recognize fluoride anion (F(-)) among other halides. This additional function is now added to its already reported organocatalytic and organogelator properties. The signaling mechanism relies on the formation of a charge-transfer (CT) complex between the urea-based sensor and F¯ in the ground state with a high association constant as demonstrated by absorption and fluorescence spectroscopy. The nature of the hydrogen bonding interaction between the sensor and F¯ was established by ¹H-NMR studies and theoretical calculations. Moreover, the recovery of the sensor was achieved by addition of methanol.
Theoretical Study of Wave Breaking for Nonlinear Water Waves Propagating on a Sloping Bottom
Chen, Y. Y.; Hsu, H. C.; Li, M. S.
2012-04-01
In this paper, a third-order asymptotic solution in a Lagrangian framework describing nonlinear water wave propagation on the surface of a uniform sloping bottom is presented. A two-parameter perturbation method is used to develop a new mathematical derivation. The particle trajectories, wave pressure and Lagrangian velocity potential are obtained as a function of the nonlinear wave steepness and the bottom slope perturbed to third order. This theoretical solution in Lagrangian form satisfies state of the normal pressure at the free surface. The condition of the conservation of mass flux is examined in detail for the first time. The two important properties in Lagrangian coordinates, Lagrangian wave frequency and Lagrangian mean level, are included in the third-order solution. The solution can also be used to estimate the mean return current for waves progressing over the sloping bottom. The Lagrangian solution untangle the description of the features of wave shoaling in the direction of wave propagation from deep to shallow water, as well as the process of successive deformation of a wave profile and water particle trajectories leading to wave breaking. A series of experiment was conducted to validate the obtained theoretical solution. The proposed solution will be used to determine the wave shoaling and breaking process and the comparisons between the experimental and theoretical results are excellent. For example, the variations of phase velocity on sloping bottom are obtained by 7 set of two close wave gauges and the theoretical result could accurately predict the measured phase velocity. The theoretical wave breaking index can be derived by use of the kinematic stability parameter (K.P.S). The comparisons between the theory, experiment (present study, Iwagali et al.(1974), Deo et al.(2003) and Tsai et al.(2005)) and empirical formula of Goda (2004) for the breaking index(u/C) versus the relative water depth(d/L) under two different bottom slopes shows that the
Theoretical modelling of photoactive molecular systems: insights using the Density Functional Theory
Energy Technology Data Exchange (ETDEWEB)
Ciofini, I.; Adamo, C. [Ecole Nationale Superieure de Chimie de Paris, Lab. d' Electrochimie et Chimie Analytique, CNRS UMR 7575, 75 - Paris (France); Laine, Ph.P. [Universite Rene-Descartes, Lab. de Chimie et Biochimie Pharmacologiques et Toxicologiques, CNRS UMR 8601, 75 - Paris (France); Bedioui, F. [Ecole Nationale Superieure de Chimie de Paris, Lab. de Pharmacologie Chimique et Genetique, CNRS FRE 2463 and INSERM U 640, 75 - Paris (France); Daul, C.A. [Fribourg Univ., Dept. de Chimie (Switzerland)
2006-02-15
An account of the performance of a modern and efficient approach to Density Functional Theory (DFT) for the prediction of the photophysical behavior of a series of Ru(II) and Os(II) complexes is given. The time-dependent-DFT method was used to interpret their electronic spectra. Two different types of compounds have been analyzed: (1) a complex undergoing a light induced isomerization of one of its coordination bonds; (2) an inorganic dyads expected to undergo intramolecular photoinduced electron transfer to form a charge separated (CS) sate. Besides the noticeable quantitative agreement between computed and experimental absorption spectra, our results allow to clarify, by first principles, both the nature of the excited states and the photochemical behavior of these complex systems, thus underlying the predictive character of the theoretical approach. (authors)
Theoretical study of ferroelectric nanoparticles using phase reconstructed electron microscopy
DEFF Research Database (Denmark)
Phatak, C.; Petford-Long, A. K.; Beleggia, Marco
2014-01-01
Ferroelectric nanostructures are important for a variety of applications in electronic and electro-optical devices, including nonvolatile memories and thin-film capacitors. These applications involve stability and switching of polarization using external stimuli, such as electric fields. We present...... a theoretical model describing how the shape of a nanoparticle affects its polarization in the absence of screening charges, and quantify the electron-optical phase shift for detecting ferroelectric signals with phase-sensitive techniques in a transmission electron microscope. We provide an example phase shift...
Theoretical study of the thermochemistry of chlorine oxyfluorides
Sánchez, Hernán R.; Del Pla, Julián
2016-10-01
There is a lack of experimental thermochemical values for most chlorine oxyfluorides. Previous high level theoretical, CCSD(T), results showed uncommonly large errors in the standard heats of formation calculated through the atomization method. We propose that the differences are due to unusually large contributions to energy from higher excitations within the coupled cluster framework, and we tackle the problem by using a calculation scheme based on isodesmic reactions. Our suspicions are supported by results of static correlation diagnostics. Our final recommended values are in better agreement with the experimental data available. Other thermodynamic properties are also calculated.
Experimental and theoretical study on rapid transient nucleated boiling
Institute of Scientific and Technical Information of China (English)
无
2001-01-01
A laser heater has been used to impose a pulsed high power laser beam on a metal film inunersed in liquid to generate a very high rate of temperature rise up to 9.3 × 106K/s in the metal film. The rapid transient boiling phenomena have been observed and the temperature variations in the metal film have been measured. Theoretical calculations have been carried out with the fluctuation nucleation theory and the heat conduction theory to compare with the experimental results, and some results are reported.
Directory of Open Access Journals (Sweden)
2016-12-01
Full Text Available Dissociative identity disorder [DID] is a chronic complex psychiatric condition related to cumulative psychological traumatization in childhood. It is characterized by a marked disturbance of identity due to the presence of distinct personality states and repetitive dissociative amnesias which interfere with the continuity of the affected persons autobiography. These personality states [alter personalities] recurrently take control of or influence the individual undermining one’s sense of self and agency. Although working with alter personalities is the hallmark of psychotherapy in DID, a detailed and specific clinical and theoretical psychopathology of alter personalities do not exist yet. Hence, the present paper addresses the formation and functions of alter personalitiesin DID. The hypotheses, proposals, andassumptions developed in this paper have been derived from experiences inintensive treatment of a very large number of patients with DID over more than two decades. The authors propose that the reconciliation between diverse perspectives about one’s internal world and external reality carried by various personalities is necessary for successful treatment of DID. The hallmark of dealing with alter and host personalities constitutes of the elimination of misperceptions of themabout each other personality state and even about themselves.This requires an analysis of the missions and functions of alter personalities which are usually different thanthe perceived conceptualizations.This recognition usually increases the therapeutic alliance and even consent between the therapist, and alter and host personalities and decreases the duration of treatment. The present paper is a preliminary one on this subject and may serve as a basis both for further theoretical elaborations as well as for development of hypotheses in empirical research devoted to understanding operations of human mind when exposed to stress in particular as well as the
Yildirim, G; Senol, S D; Dogruer, M; Ozturk, O; Senol, A; Tasci, A T; Terzioglu, C
2012-01-01
This study reports the optimized molecular structures, vibrational frequencies including Infrared intensities and Raman activities, corresponding vibrational assignments, (1)H and (13)C NMR chemical shifts, the magnitudes of the JCH and JCC coupling constants, Ultraviolet-visible (UV-vis) spectra, thermodynamic properties and atomic charges of the title compounds, α,α,α-trifluoro-3, -p and o-nitrotoluene, in the ground state by means of the density functional theory (DFT) with the standard B3LYP/6-311++G(d,p) method and basis set combination for the first time. Theoretical vibrational spectra were interpreted by normal coordinate analysis based on scaled density functional force field. The results show that the vibrational frequencies and chemical shifts calculated were obtained to be in good agreement with the experimental data. Based on the comparison between experimental results and theoretical data, the calculation level chosen is powerful approach for understanding the identification of all the molecules studied. In addition, not only were frontier molecular orbitals (HOMO and LUMO), molecular electrostatic potential (MEP) and electrostatic potential (ESP) simulated but also the dipole moment, softness, electronegativity, chemical hardness, electrophilicity index, transition state and energy band gap values were predicted. According to the investigations, all compounds were found to be useful to bond metallically and interact intermolecularly; however, the thermodynamic properties confirm that the α,α,α-trifluoro-p-nitrotoluene was more reactive and more polar than the others.
Yildirim, G.; Senol, S. D.; Dogruer, M.; Ozturk, O.; Senol, A.; Tasci, A. T.; Terzioglu, C.
2012-01-01
This study reports the optimized molecular structures, vibrational frequencies including Infrared intensities and Raman activities, corresponding vibrational assignments, 1H and 13C NMR chemical shifts, the magnitudes of the JCH and JCC coupling constants, Ultraviolet-visible (UV-vis) spectra, thermodynamic properties and atomic charges of the title compounds, α,α,α-trifluoro-3, -p and o-nitrotoluene, in the ground state by means of the density functional theory (DFT) with the standard B3LYP/6-311++G(d,p) method and basis set combination for the first time. Theoretical vibrational spectra were interpreted by normal coordinate analysis based on scaled density functional force field. The results show that the vibrational frequencies and chemical shifts calculated were obtained to be in good agreement with the experimental data. Based on the comparison between experimental results and theoretical data, the calculation level chosen is powerful approach for understanding the identification of all the molecules studied. In addition, not only were frontier molecular orbitals (HOMO and LUMO), molecular electrostatic potential (MEP) and electrostatic potential (ESP) simulated but also the dipole moment, softness, electronegativity, chemical hardness, electrophilicity index, transition state and energy band gap values were predicted. According to the investigations, all compounds were found to be useful to bond metallically and interact intermolecularly; however, the thermodynamic properties confirm that the α,α,α-trifluoro-p-nitrotoluene was more reactive and more polar than the others.
Dong, Ren G.; Welcome, Daniel E.; McDowell, Thomas W.; Wu, John Z.
2015-01-01
While simulations of the measured biodynamic responses of the whole human body or body segments to vibration are conventionally interpreted as summaries of biodynamic measurements, and the resulting models are considered quantitative, this study looked at these simulations from a different angle: model calibration. The specific aims of this study are to review and clarify the theoretical basis for model calibration, to help formulate the criteria for calibration validation, and to help appropriately select and apply calibration methods. In addition to established vibration theory, a novel theorem of mechanical vibration is also used to enhance the understanding of the mathematical and physical principles of the calibration. Based on this enhanced understanding, a set of criteria was proposed and used to systematically examine the calibration methods. Besides theoretical analyses, a numerical testing method is also used in the examination. This study identified the basic requirements for each calibration method to obtain a unique calibration solution. This study also confirmed that the solution becomes more robust if more than sufficient calibration references are provided. Practically, however, as more references are used, more inconsistencies can arise among the measured data for representing the biodynamic properties. To help account for the relative reliabilities of the references, a baseline weighting scheme is proposed. The analyses suggest that the best choice of calibration method depends on the modeling purpose, the model structure, and the availability and reliability of representative reference data. PMID:26740726
Scaling properties of information-theoretic quantities in density functional reactivity theory.
Rong, Chunying; Lu, Tian; Ayers, Paul W; Chattaraj, Pratim K; Liu, Shubin
2015-02-21
Density functional reactivity theory (DFRT) employs the electron density and its related quantities to describe reactivity properties of a molecular system. Quantities from information theory such as Shannon entropy, Fisher information, and Ghosh-Berkowitz-Parr entropy are natural descriptors within the DFRT framework. They have been previously employed to quantify electrophilicity, nucleophilicity and the steric effect. In this work, we examine their scaling properties with respect to the total number of electrons. To that end, we considered their representations in terms of both the electron density and the shape function for isolated atoms and neutral molecules. We also investigated their atomic behaviors in different molecules with three distinct partitioning schemes: Bader's zero-flux, Becke's fuzzy atom, and Hirshfeld's stockholder partitioning. Strong linear relationships of these quantities as a function of the total electron population are reported for atoms, molecules, and atoms in molecules. These relationships reveal how these information-theoretic quantities depend on the molecular environment and the electron population. These trends also indicate how these quantities can be used to explore chemical reactivity for real chemical processes.
Singlet oxygen reactions with flavonoids. A theoretical-experimental study.
Directory of Open Access Journals (Sweden)
Javier Morales
Full Text Available Detection of singlet oxygen emission, λ(max = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, k(T, and the reactive reaction rate constant, k(r, for the reaction between singlet oxygen and several flavonoids. Values of k(T determined in deuterated water, ranging from 2.4×10(7 M(-1 s(-1 to 13.4×10(7 M(-1 s(-1, for rutin and morin, respectively, and the values measured for k(r, ranging from 2.8×10(5 M(-1 s(-1 to 65.7×10(5 M(-1 s(-1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid.
Singlet Oxygen Reactions with Flavonoids. A Theoretical – Experimental Study
Morales, Javier; Günther, Germán; Zanocco, Antonio L.; Lemp, Else
2012-01-01
Detection of singlet oxygen emission, λmax = 1270 nm, following laser excitation and steady-state methods were employed to measure the total reaction rate constant, kT, and the reactive reaction rate constant, kr, for the reaction between singlet oxygen and several flavonoids. Values of kT determined in deuterated water, ranging from 2.4×107 M−1s−1 to 13.4×107 M−1s−1, for rutin and morin, respectively, and the values measured for kr, ranging from 2.8×105 M−1s−1 to 65.7×105 M−1s−1 for kaempferol and morin, respectively, being epicatechin and catechin chemically unreactive. These results indicate that all the studied flavonoids are good quenchers of singlet oxygen and could be valuable antioxidants in systems under oxidative stress, in particular if a flavonoid-rich diet was previously consumed. Analysis of the dependence of rate constant values with molecular structure in terms of global descriptors and condensed Fukui functions, resulting from electronic structure calculations, supports the formation of a charge transfer exciplex in all studied reactions. The fraction of exciplex giving reaction products evolves through a hydroperoxide and/or an endoperoxide intermediate produced by singlet oxygen attack on the double bond of the ring C of the flavonoid. PMID:22802966
Theoretical Study of Interplay Between Superconductivity and Itinerant Ferromagnetism
Directory of Open Access Journals (Sweden)
Subhra Kakani
2014-08-01
Full Text Available Following Green’s function technique and equation of motion method, the coexistence of superconductivity (SC and itinerant ferromagnetism (FM is investigated in a single band homogenous system. Self consistent equations for SC and FM order parameters, Δ and m or I respectively are derived. It is shown that there generally exists a coexistent (Δ ≠ 0, and m or I ≠ 0 solutions to the coupled equations of the order parameter in the, temperature range 0 < T < min(TC, TFM, where TC and TFM are respectively the superconducting and ferromagnetic transition temperatures. Expressions for specific heat, density of states, free energy and critical field are derived. The specific heat has linear temperature dependence as opposed to the exponential decrease in the BCS theory. The density of states for a finite m increases as opposed to that of a ferromagnetic metal. Free energy study reveals that FMSC state has lowest energy than the normal FM state and therefore realized at low enough temperature .Effect of small external field is also studied. The theory is applied to explain the observations in uranium based intermetallics systems UCoGe and UIr. The agreement between theory and experiments is quite encouraging.
Theoretical Study on Inner Shell Electron Impact Excitation of Lithium
Institute of Scientific and Technical Information of China (English)
YANG Ning-Xuan; DONG Chen-Zhong; JIANG Jun
2009-01-01
Cross sections for electron impact excitation of lithium from the ground state ls22s to the excited states 1s2s2,1s2p2,1s2snp (n = 2-5),1s2sns (n = 3-5),1s2pns (n = 3-5),and 1s2pnp (n=3-5) are calculated by using a full relativistic distorted wave method.The latest experimental electron energy loss spectra for inner-shell electron excitations of lithium at a given incident electron energy of 2500 eV[Chin.Phys.Lett.25 (2008) 3649]have been reproduced by the present theoretical investigation excellently.At the same time,the structures of electron energy loss spectra of lithium at low incident electron energy are also predicted theoretically,it is found that the electron energy loss spectra in the energy region of 55-57eV show two-peak structures.
Protonation of caffeine: A theoretical and experimental study
Energy Technology Data Exchange (ETDEWEB)
Bahrami, Hamed [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of); Tabrizchi, Mahmoud, E-mail: m-tabriz@cc.iut.ac.ir [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of); Farrokhpour, Hossein [Department of Chemistry, Isfahan University of Technology, Isfahan 84156-83111 (Iran, Islamic Republic of)
2013-03-29
Highlights: ► Protonation of caffeine was examined by ion mobility spectrometry equipped with two ionization sources. ► Experimental and theoretical evidence was collected to assign the observed peaks to caffeine related ionic species. ► A new concept of “internal proton affinity”, the protonation tendency for each atom in a molecule, was defined. - Abstract: Protonation of caffeine was examined by ion mobility spectrometry equipped with two ionization sources, corona discharge (CD) and UV photoionization. Three peaks were observed in ion mobility spectrum by simultaneously running the two ionization sources. Experimental and theoretical evidence was collected to link the observed peaks to caffeine related ionic species. One peak was attributed to the M{sup +} ion while the other two were assigned to different protonated isomers of caffeine. In the case of CD ionization source, it was observed that different sites of caffeine compete for protonation and their relative intensities, depends on the sample concentration as well as the nature of the reactant ions. The new concept of “internal proton affinity” (IPA) was defined to express the tendency of holding the added proton for each atom in a molecule.
Energy Technology Data Exchange (ETDEWEB)
Khan, Shehryar, E-mail: sherkhan@fysik.su.se; Odelius, Michael, E-mail: odelius@fysik.su.se [Department of Physics, Stockholm University, AlbaNova University Center, S-106 91 Stockholm (Sweden); Kubica-Misztal, Aleksandra [Institute of Physics, Jagiellonian University, ul. Reymonta 4, PL-30-059 Krakow (Poland); Kruk, Danuta [Faculty of Mathematics and Computer Science, University of Warmia and Mazury in Olsztyn, Sloneczna 54, Olsztyn PL-10710 (Poland); Kowalewski, Jozef [Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University, S-106 91 Stockholm (Sweden)
2015-01-21
The zero-field splitting (ZFS) of the electronic ground state in paramagnetic ions is a sensitive probe of the variations in the electronic and molecular structure with an impact on fields ranging from fundamental physical chemistry to medical applications. A detailed analysis of the ZFS in a series of symmetric Gd(III) complexes is presented in order to establish the applicability and accuracy of computational methods using multiconfigurational complete-active-space self-consistent field wave functions and of density functional theory calculations. The various computational schemes are then applied to larger complexes Gd(III)DOTA(H{sub 2}O){sup −}, Gd(III)DTPA(H{sub 2}O){sup 2−}, and Gd(III)(H{sub 2}O){sub 8}{sup 3+} in order to analyze how the theoretical results compare to experimentally derived parameters. In contrast to approximations based on density functional theory, the multiconfigurational methods produce results for the ZFS of Gd(III) complexes on the correct order of magnitude.
Paffenholz, Joseph; Fox, Jon W.; Gu, Xiaobai; Jewett, Greg S.; Datta, Subhendu K.
1990-01-01
Scattering of Rayleigh-Lamb waves by a normal surface-breaking crack in a plate has been studied both theoretically and experimentally. The two-dimensionality of the far field, generated by a ball impact source, is exploited to characterize the source function using a direct integration technique. The scattering of waves generated by this impact source by the crack is subsequently solved by employing a Green's function integral expression for the scattered field coupled with a finite element representation of the near field. It is shown that theoretical results of plate response, both in frequency and time, are similar to those obtained experimentally. Additionally, implication for practical applications are discussed.
Theoretical study of the relativistic molecular rotational g-tensor
Energy Technology Data Exchange (ETDEWEB)
Aucar, I. Agustín, E-mail: agustin.aucar@conicet.gov.ar; Gomez, Sergio S., E-mail: ssgomez@exa.unne.edu.ar [Institute for Modeling and Technological Innovation, IMIT (CONICET-UNNE) and Faculty of Exact and Natural Sciences, Northeastern University of Argentina, Avenida Libertad 5400, W3404AAS Corrientes (Argentina); Giribet, Claudia G.; Ruiz de Azúa, Martín C. [Physics Department, Faculty of Exact and Natural Sciences, University of Buenos Aires and IFIBA CONICET, Ciudad Universitaria, Pab. I, 1428 Buenos Aires (Argentina)
2014-11-21
An original formulation of the relativistic molecular rotational g-tensor valid for heavy atom containing compounds is presented. In such formulation, the relevant terms of a molecular Hamiltonian for non-relativistic nuclei and relativistic electrons in the laboratory system are considered. Terms linear and bilinear in the nuclear rotation angular momentum and an external uniform magnetic field are considered within first and second order (relativistic) perturbation theory to obtain the rotational g-tensor. Relativistic effects are further analyzed by carrying out the linear response within the elimination of the small component expansion. Quantitative results for model systems HX (X=F, Cl, Br, I), XF (X=Cl, Br, I), and YH{sup +} (Y=Ne, Ar, Kr, Xe, Rn) are obtained both at the RPA and density functional theory levels of approximation. Relativistic effects are shown to be small for this molecular property. The relation between the rotational g-tensor and susceptibility tensor which is valid in the non-relativistic theory does not hold within the relativistic framework, and differences between both molecular parameters are analyzed for the model systems under study. It is found that the non-relativistic relation remains valid within 2% even for the heavy HI, IF, and XeH{sup +} systems. Only for the sixth-row Rn atom a significant deviation of this relation is found.
REGIONAL INNOVATION SYSTEM: THEORETICAL APPROACH AND EMPIRICAL STUDY OF CHINA
Institute of Scientific and Technical Information of China (English)
LIU Shu-guang; CHEN Cai
2003-01-01
Regional innovation system (RIS) is the new research field of modern economic geography in the age of knowledge economy. Based on the researches of regional economic geography, the authors of the paper consider RIS as the integrated and interactive systems with innovation milieu, elements, units, structure and functions. Five aspects of evaluation indicators including innovation input scale and output scale, innovation milieu transition, innovation in-ner operation, as well as innovation outer impact are worked out for final indicators of RIS scale and quality. Accord-ing to different RIS situations, three patterns of independent, imitative and cooperative development are put forward for choosing. At the latter part of the paper, we select 12 provincial regions (including three municipalities and one au-tonomous region) of China for empirical study. The results show that there exists great difference among each region from the aspects of innovation scale and quality mainly owning to the diversification of RIS social and economic mi-lieu, the major innovative units of enterprises, universities and R&D institutes. Finally, the paper points out the innova-tion development decisions for each region.
Graphene to fluorographene and fluorographane: a theoretical study.
Paupitz, R; Autreto, P A S; Legoas, S B; Srinivasan, S Goverapet; van Duin, A C T; Galvão, D S
2013-01-25
We report here a fully reactive molecular dynamics study on the structural and dynamical aspects of the fluorination of graphene membranes (fluorographene). Our results show that fluorination tends to produce defective areas on the graphene membranes with significant distortions of carbon-carbon bonds. Depending on the amount of incorporated fluorine atoms, large membrane holes were observed due to carbon atom losses. These results may explain the broad distribution of the structural lattice parameter values experimentally observed. We have also investigated the effects of mixing hydrogen and fluorine atoms on the graphene functionalization. Our results show that, when in small amounts, the presence of hydrogen atoms produces a significant decrease in the rate of fluorine incorporation onto the membrane. On the other hand, when fluorine is the minority element, it produces a significant catalytic effect on the rate of hydrogen incorporation. We have also observed the spontaneous formation of new hybrid structures with different stable configurations (chair-like, zigzag-like and boat-like) which we named fluorographane.
Theoretical studies on energetic materials bearing pentaflurosulphyl (SF5) groups
Indian Academy of Sciences (India)
Li Xiao-Hong; Cui Hong-Ling; Ju Wei-Wei; Li Tong-Wei; Zhang Rui-Zhou; Yong Yong-Liang
2014-07-01
Heats of formation (HOF) for a series of energetic materials containing SF5 group were studied by density functional theory. Results show that HOFs increase with the augmention of field effects of substituted groups. Addition of furazan or furoxan ring increases HOF of the energetic materials. All the SF5-containing compounds have densities which are ∼0.19 g/cm3 higher than those containing -NH2 group. S-F bond is the trigger bond for the thermolysis process in the title compounds and bond dissociation energies of the weakest bonds range from 351.1 to 388.3 kJ/mol. Detonation velocities (D) and pressures (P) are evaluated by Kamlet-Jacobs equations with the calculated densities and HOFs. Results show that increasing the amount of furazan rings results in a larger D and P. Considering the detonation performance and thermal stability, eight compounds may be considered as potential candidates for high-energy density materials.
Theoretical study of nonlinear optical properties of some azoic dyes
Directory of Open Access Journals (Sweden)
Hadji Djebar
2015-07-01
Full Text Available In this paper we presented semi-empirical PM3, ab-initio (HF, MP2 and DFT (B3LYP, B3PW91 calculation of the dipole moment, polarizability, and first hyperpolarizability of some azoics dyes derivatives which have electron donor and electron acceptor groups on either sides. The first hyperpolarizability of these molecules was calculated with PM3 method, HF/6-31G**, HF/6-31+G**, HF/6-31++G**, DFT with B3LYP and B3PW91 functional, and MP2/6-31++G** based on finite field approach using GAUSSIAN03 program. The effects of the intramolecular charge transfer (ICT from the donor to the acceptor groups on the molecular geometry and atomic charge distribution of these NLO chromophores are derived from its HF, MP2 and DFT calculations. The variation of this property has also been correlated to E (HOMO-LUMO gap and to the nature of the highest occupied molecular orbital HOMO and the lowest unoccupied molecular orbital HOMO. The study reveals that the azoics dyes derivatives have large hyperpolarizability values; hence they may be used in the development of nonlinear optical materials.
Theoretical Study on the High Energy Density Compound Hexanitrohexaazatricyclotetradecanedifuroxan
Institute of Scientific and Technical Information of China (English)
QIU Ling; XIAO He-Ming; ZHU Wei-Hua; JU Xue-Hai; GONG Xue-Dong
2006-01-01
Density functional theory (DFT) has been employed to study the molecular geometries, electronic structures,infrared (IR) spectra, and thermodynamic properties of the high energy density compound hexanitrohexaazatricyclotetradecanedifuroxan (HHTTD) at the B3LYP/6-31G** level of theory. The calculated results showthattherearefourconformationalisomers (a, β, γ and δ) for HHTTD, and the relative stabilities of four conformers were assessed based on the calculated total energies and the energy-gaps between the frontier molecular orbitals. The computed harmonic vibrational frequencies are in reasonable agreement with the available experimental data. Thermodynamic properties derived from the IR spectra on the basis of statistical thermodynamic principles are linearly correlated with the temperature. Detonation performances were evaluated by using the Kamlet-Jacobsequationsbasedonthecalculated densities and heats of formation. It was found that four HHTTD isomers with the predicted densities of ca. 2 g·cm-3, detonation velocities near 10 km·s-1, and detonation pressures over 45 Gpa, may be novel potential candidates of high energy density materials (HEDM). These results may provide basic information for the molecular designof HEDM.
Theoretical study of selective methylation in the synthesis of azithromycin
Duran, Dilek; Aviyente, Viktorya; Baysal, Canan
2004-01-01
Azithromycin is a 15-membered macrolide antibiotic which is active in vitro against clinically important gram-negative bacteria. In this study, the selectivity of the methylation mechanism was analyzed computationally on the 2'- OCbz-3'- NMeCbz derivative of azithromycin in vacuum and in DMF. We have shown that the methylation of the hydroxy group on C-6 is energetically unfavorable compared to the other hydroxy groups in vacuum; the softness values further showed that the C-6 anion is not reactive towards CH3I in the methylation mechanism. To understand the effect of the solvent on the methylation process, detailed molecular dynamics simulations were performed in DMF using the anions at the C-4'', C-6, C-11 and C-12 positions. We find the conformations of the anions not to be affected by the presence of the solvent. The radial distribution functions of the solvent molecules around the O- of the anions demonstrate that DMF molecules cluster around the C-6 anion. The relative strength of the anion-solvent interactions reveal that the solvent molecules provide the largest stabilization to the C-6 anion and prevent the methylation at this position. The latter descriptor was found to be an important factor in explaining the experimentally observed selectivity towards the methylation of the C-4'', C-6, C-11 and C-12 anions.
Theoretical and numerical studies on morphological transitions in crack growth
Mühle, V
1999-01-01
This paper investigates the formation of crack patterns in stationary and transient temperature fields analytically with linear elastic fracture mechanics and numerically with the finite elements method (FEM). In particular, we consider the experimental situation of a narrow thin strip of hot glass slowly lowered into cold water, with temperature difference and velocity as variable parameters. The parameter regions of no crack, one straight crack and one oscillating crack are determined. The type of phase transition related to the borderline between straight and oscillating crack is characterized. The theoretical results are compared with those of other Similar investigations and comparisons are done for the propagation of multiple cracks. Quenching of a wide thin strip leads to a hierarchy of cracks whose scaling properties are analyzed. Without any fitting, theory and experiment agree surprisingly well.
Protonation of caffeine: A theoretical and experimental study
Bahrami, Hamed; Tabrizchi, Mahmoud; Farrokhpour, Hossein
2013-03-01
Protonation of caffeine was examined by ion mobility spectrometry equipped with two ionization sources, corona discharge (CD) and UV photoionization. Three peaks were observed in ion mobility spectrum by simultaneously running the two ionization sources. Experimental and theoretical evidence was collected to link the observed peaks to caffeine related ionic species. One peak was attributed to the M+ ion while the other two were assigned to different protonated isomers of caffeine. In the case of CD ionization source, it was observed that different sites of caffeine compete for protonation and their relative intensities, depends on the sample concentration as well as the nature of the reactant ions. The new concept of "internal proton affinity" (IPA) was defined to express the tendency of holding the added proton for each atom in a molecule.
Theoretical study on a solar collector loop during stagnation
DEFF Research Database (Denmark)
Chen, Ziqian; Dragsted, Janne; Furbo, Simon;
2010-01-01
A mathematical model simulating the stagnation behavior of a pressurized solar collector loop with solar collectors with a good emptying behavior is developed. Based on the pre-pressure of the expansion vessel, the system filling pressure of the solar collector loop and the design of the solar...... collector loop, the mass of the fluid flowing into the pressurized expansion vessel and the pressures at the top part and at the bottom part of the solar collector loop during stagnation for the solar collector loop are calculated. The theoretically calculated results are compared with experimental results....... There is a good agreement between calculations and measurements. The developed simulation model is therefore suitable to determine the behavior of solar collector loops during stagnation....
Theoretical study on a solar collector loop during stagnation
DEFF Research Database (Denmark)
Chen, Ziqian; Dragsted, Janne; Furbo, Simon;
A mathematical model simulating the stagnation behavior of a pressurized solar collector loop with solar collectors with a good emptying behavior is developed. Based on the pre-pressure of the expansion vessel, the system filling pressure of the solar collector loop and the design of the solar...... collector loop, the mass of the fluid flowing into the pressurized expansion vessel and the pressures at the top part and at the bottom part of the solar collector loop during stagnation for the solar collector loop are calculated. The theoretically calculated results are compared with experimental results....... There is a good agreement between calculations and measurements. The developed simulation model is therefore suitable to determine the behavior of solar collector loops during stagnation....
Theoretical Advanced Study Institute in Elementary Particle Physics
2017-01-01
The program will consist of a pedagogical series of lectures and seminars. Lectures will be given over a four-week period, three or four lectures per day, Monday through Friday. The audience will be composed primarily of advanced theoretical graduate students. Experimentalists with a strong background in theory are also encouraged to apply. Some post-doctoral fellows will be admitted, but preference will be given to applicants who will not have received their Ph.D. before 2017. The minimum background needed to get full benefit of TASI is a knowledge of quantum field theory (including RGEs) and familiarity with the Standard Model. Some familiarity with SUSY would be helpful. We hope to provide some subsidy, but students will need partial support from other sources. Rooms, meals, and access to all facilities will be provided at reasonable rates in beautifully located dormitories at the University of Colorado.
Theoretical study about L-arginine complexes formation with thiotriazolin
Directory of Open Access Journals (Sweden)
L. I. Kucherenko
2017-02-01
Full Text Available Brain vascular diseases are one of the leading causes of morbidity, mortality and disability of population in the industrialized countries of the world. An important element of this problem’s solution is the creation of new highly effective and safe drugs, which would lead to mortality reduction, to increase in life expectancy and quality of life. Therefore it is interesting to create a new combined drug based on L-arginine and thiotriazolin. Purpose of the study: to consider the possible structure and energy characteristics of complexes formed by L-arginine, 3-methyl-1,2,4-triazolyl-5-thioacetate (MTTA and morpholine. Calculation method. The initial approximation to the complex geometry was obtained using molecular docking with the help of AutoDock Vina program. The obtained ternary complexes were pre-optimized by semi-empirical PM7 method with modeling the impact of the environment by COSMO method. The calculations were carried out using MOPAC2012 program. Then they were optimized by B97-D3/SVP + COSMO (Water dispersion-corrected DFT-D with geometrical spreading correction on insufficiency of gCP basis set. A more accurate calculation of the solvation energy was conducted by SMD. The calculations by density functional method were carried out using the ORCA 3.0.3 software. Energy complex formation in solution was calculated as the difference of the Gibbs free energy of the solvated complex and its individual components. Results. Quantum chemical calculations show, that thiotriazolin and L-arginine are able to form ternary complexes, where molecules are linked by multiple hydrogen bonds. The calculation data suggest, that studied complexes are thermodynamically unstable in solution. The energies of them are positive, but rather low despite charge gain of a number of intermolecular hydrogen bonds. Finding. Based on the results of the conducted quantum-chemical study of a three components system (MTTA, morpholine, and L-arginine it is possible
The Theoretical Approaches to Defining the Essence and Functions of Leasing
Directory of Open Access Journals (Sweden)
Levchenko Alexander A.
2017-03-01
Full Text Available The article is aimed at researching the theoretical foundations, generalizing scientific approaches to interpretation of the concept of «leasing», defining the main economic characteristics and functions of leasing. Scientific approaches of researchers to definition of the concept of «leasing» were systematized. New scientific approaches to interpretation of the concept of leasing as a form of public-private partnership, a form of ensuring competitiveness, have been allocated. The author’s own point of view on defining the economic essence of leasing as a special type of entrepreneurial activity which at the same time is implemented in the form of the credit-investment along with the trade-property relations has been substantiated. The main functions of leasing according to the object and subject approach in terms of outsourcing have been disclosed. Further researches in this direction will concern systematization of scientific approaches and definition of new attributes of the specific classification of leasing.
Cheng, Jierong; Wang, Wei Li; Mosallaei, Hossein; Kaxiras, Efthimios
2014-01-08
Graphene was recently shown to support deep subwavelength surface plasmons at terahertz frequencies characterized by low energy loss and strong field localization, both highly desirable. The properties of graphene can be locally tuned by applying an external gate voltage or by the adsorption of organic molecules that lead to doping through charge transfer. Local tuning of the electronic features of graphene opens the possibility to realize any desired gradient index profile and thus brings large flexibility to control and manipulate the propagation of surface plasmons. Here, we explore this possibility created by functionalizing graphene with organic molecules. We employ a multiscale theoretical approach that combines first-principles electronic structure calculations and finite-difference time-domain simulations coupled by surface conductivity. We show that by patterning two types of organic molecules on graphene, a plasmonic metasurface can be realized with any gradient effective refractive index profile to manipulate surface plasmon beams as desired. The special properties of such devices based on functionalized graphene are compared to the similar metamaterials based on metallic films on top of a gradient index dielectric substrate. Using this idea, we design and analyze an ultrathin broadband THz plasmonic lens as proof-of-concept, while more sophisticated index profiles can also be realized and various plasmonic applications are readily accessible.
Theoretical study on the reactivity of sulfate species with hydrocarbons
Ma, Q.; Ellis, G.S.; Amrani, A.; Zhang, T.; Tang, Y.
2008-01-01
The abiotic, thermochemically controlled reduction of sulfate to hydrogen sulfide coupled with the oxidation of hydrocarbons, is termed thermochemical sulfate reduction (TSR), and is an important alteration process that affects petroleum accumulations in nature. Although TSR is commonly observed in high-temperature carbonate reservoirs, it has proven difficult to simulate in the laboratory under conditions resembling nature. The present study was designed to evaluate the relative reactivities of various sulfate species in order to provide greater insight into the mechanism of TSR and potentially to fill the gap between laboratory experimental data and geological observations. Accordingly, quantum mechanics density functional theory (DFT) was used to determine the activation energy required to reach a potential transition state for various aqueous systems involving simple hydrocarbons and different sulfate species. The entire reaction process that results in the reduction of sulfate to sulfide is far too complex to be modeled entirely; therefore, we examined what is believed to be the rate limiting step, namely, the reduction of sulfate S(VI) to sulfite S(IV). The results of the study show that water-solvated sulfate anions SO42 - are very stable due to their symmetrical molecular structure and spherical electronic distributions. Consequently, in the absence of catalysis, the reactivity of SO42 - is expected to be extremely low. However, both the protonation of sulfate to form bisulfate anions (HSO4-) and the formation of metal-sulfate contact ion-pairs could effectively destabilize the sulfate molecular structure, thereby making it more reactive. Previous reports of experimental simulations of TSR generally have involved the use of acidic solutions that contain elevated concentrations of HSO4- relative to SO42 -. However, in formation waters typically encountered in petroleum reservoirs, the concentration of HSO4- is likely to be significantly lower than the levels
Tao, Chao; Regner, Michael F.; Zhang, Yu; Jiang, Jack J.
2014-01-01
Summary The relationship between the vocal fold elongation and the phonation threshold pressure (PTP) was experimentally and theoretically investigated. The PTP values of seventeen excised canine larynges with 0% to 15% bilateral vocal fold elongations in 5% elongation steps were measured using an excised larynx phonation system. It was found that twelve larynges exhibited a monotonic relationship between PTP and elongation; in these larynges, the 0% elongation condition had the lowest PTP. Five larynges exhibited a PTP minimum at 5% elongation. To provide a theoretical explanation of these phenomena, a two-mass model was modified to simulate vibration of the elongated vocal folds. Two pairs of longitudinal springs were used to represent the longitudinal elastin in the vocal folds. This model showed that when the vocal folds were elongated, the increased longitudinal tension would increase the PTP value and the increased vocal fold length would decrease the PTP value. The antagonistic effects contributed by these two factors were found to be able to cause either a monotonic or a non-monotonic relationship between PTP and elongation, which were consistent with experimental observations. Because PTP describes the ease of phonation, this study suggests that there may exist a nonzero optimal vocal fold elongation for the greatest ease for phonation in some larynges. PMID:25530744
We need theoretical physics approaches to study living systems
Blagoev, Krastan B.; Shukla, Kamal; affil="3" >Herbert Levine,
2013-08-01
Living systems, as created initially by the transition from assemblies of large molecules to self-reproducing information-rich cells, have for centuries been studied via the empirical toolkit of biology. This has been a highly successful enterprise, bringing us from the vague non-scientific notions of vitalism to the modern appreciation of the biophysical and biochemical bases of life. Yet, the truly mind-boggling complexity of even the simplest self-sufficient cells, let alone the emergence of multicellular organisms, of brain and consciousness, and to ecological communities and human civilizations, calls out for a complementary approach. In this editorial, we propose that theoretical physics can play an essential role in making sense of living matter. When faced with a highly complex system, a physicist builds simplified models. Quoting Philip W Anderson's Nobel prize address, 'the art of model-building is the exclusion of real but irrelevant parts of the problem and entails hazards for the builder and the reader. The builder may leave out something genuinely relevant and the reader, armed with too sophisticated an experimental probe, may take literally a schematized model. Very often such a simplified model throws more light on the real working of nature....' In his formulation, the job of a theorist is to get at the crux of the system by ignoring details and yet to find a testable consequence of the resulting simple picture. This is rather different than the predilection of the applied mathematician who wants to include all the known details in the hope of a quantitative simulacrum of reality. These efforts may be practically useful, but do not usually lead to increased understanding. To illustrate how this works, we can look at a non-living example of complex behavior that was afforded by spatiotemporal patterning in the Belousov-Zhabotinsky reaction [1]. Physicists who worked on this system did not attempt to determine all the relevant chemical intermediates
Directory of Open Access Journals (Sweden)
Dongling Zhan
2014-02-01
Full Text Available The thermophilic intracellular protease (PH1704 from Pyrococcus horikoshii that functions as an oligomer (hexamer or higher forms has proteolytic activity and remarkable stability. PH1704 is classified as a member of the C56 family of peptidases. This study is the first to observe that the use of Cl− as an allosteric inhibitor causes appreciable changes in the catalytic activity of the protease. Theoretical methods were used for further study. Quantum mechanical calculations indicated the binding mode of Cl− with Arg113. A molecular dynamics simulation explained how Cl− stabilized distinct contact species and how it controls the enzyme activity. The new structural insights obtained from this study are expected to stimulate further biochemical studies on the structures and mechanisms of allosteric proteases. It is clear that the discovery of new allosteric sites of the C56 family of peptidases may generate opportunities for pharmaceutical development and increases our understanding of the basic biological processes of this peptidase family.
Energy Technology Data Exchange (ETDEWEB)
Bretagne, J. (Universite de Paris-Sud, 91405 Orsay, Cedex (France)); Graham, W.G. (Physics Department, Queen' s University, Belfast (Northern Ireland)); Hopkins, M.B. (Physics Department, Dublin City University, Dublin (Ireland))
1990-08-05
Experimental and theoretical electron energy distribution functions (EEDF) measured and calculated for the driver of a multicusp ion source operating in hydrogen are compared. The results indicate that atomic physics based theoretical models can accurately predict the EEDF in such discharges if some appropriate experimentally determined quantities are used as input parameters. The magnitude and shape of the EEDF is found to be particularly sensitive to the effective surface to volume ratio for electrons.
Ohta, Shinri; Fukui, Naoki; Sakai, Kuniyoshi L
2013-01-01
The nature of computational principles of syntax remains to be elucidated. One promising approach to this problem would be to construct formal and abstract linguistic models that parametrically predict the activation modulations in the regions specialized for linguistic processes. In this article, we review recent advances in theoretical linguistics and functional neuroimaging in the following respects. First, we introduce the two fundamental linguistic operations: Merge (which combines two words or phrases to form a larger structure) and Search (which searches and establishes a syntactic relation of two words or phrases). We also illustrate certain universal properties of human language, and present hypotheses regarding how sentence structures are processed in the brain. Hypothesis I is that the Degree of Merger (DoM), i.e., the maximum depth of merged subtrees within a given domain, is a key computational concept to properly measure the complexity of tree structures. Hypothesis II is that the basic frame of the syntactic structure of a given linguistic expression is determined essentially by functional elements, which trigger Merge and Search. We then present our recent functional magnetic resonance imaging experiment, demonstrating that the DoM is indeed a key syntactic factor that accounts for syntax-selective activations in the left inferior frontal gyrus and supramarginal gyrus. Hypothesis III is that the DoM domain changes dynamically in accordance with iterative Merge applications, the Search distances, and/or task requirements. We confirm that the DoM accounts for activations in various sentence types. Hypothesis III successfully explains activation differences between object- and subject-relative clauses, as well as activations during explicit syntactic judgment tasks. A future research on the computational principles of syntax will further deepen our understanding of uniquely human mental faculties.
Theoretical study on primary reaction of photosynthetic bacteria
Institute of Scientific and Technical Information of China (English)
张纯喜; 樊红军; 李良璧; 匡廷云
1999-01-01
Theoretical calculation was carried out on the primary electron donor P870 of photosynthetic bacteria. The results show that: （ⅰ） the bimolecular structure of the primary electron donor is more advantageous in energy than monomolecular structure; （ⅱ） the initial configuration of primary electron donor is no longer stable and changes to the configuration with lower energy and chemical reactivity after the charge separation. In the P870, such structural change is completed through the rotation of C3 acetyl, so the oxygen atom of acetyl interacts with the magnesium atom of another bacterio-chlorophyll molecule, and the total energy and chemical reactivity are reduced evidently. It is suggested that the structural change of the primary electron donor is important in preventing the occurrence of charge recombination during the primary reaction and maintaining the high efficiency of the conversion of sun-light to chemical energy. A new mechanism of primary reaction has been proposed, which can give r
Solvothermal synthesis and theoretical study of a polypyridium trimesylate adduct
Indian Academy of Sciences (India)
Yulan Zhu; Feng Ma; Kuirong Ma; Li Cao; Lianhua Zhao
2011-09-01
The title compound (C9H3O6·C20H17N4)4·0.5H2O 1 was isolated from solvothermal synthesis of 4'-(4-pyridyl)-2,2':6',2'-terpyridine (pytpy) and trimesic acid (1,3,5-benzenetricarboxylic acid, H3BTC). It was characterized by element analysis, IR, TGA, XRD, X-ray single-crystal diffraction, and spectroscopy properties, together with quantum chemistry calculation of spectrum (UV-vis spectra) through the method b3lyp/6-31 t g (d,p) are also investigated. Single-crystal X-ray diffraction shows 1 possesses a 3-D supramolecular network with 1-D six-fold helical double chains built from protonated (H3pytpy)$^{3+}_{n}$ cations and deprotonated (BTC)$^{3−}_{n}$ anions. The maximum of the fluorescent emission bands of 1 is located at 427 nm (ex = 266 nm), with a shoulder at about 390 nm. The result of theoretic calculations confirms that 1 has small HOMO-LUMO energy gap (1.24 eV) and high chemical reactivity.
Theoretical and Experimental Studies of Elementary Particle Physics
Energy Technology Data Exchange (ETDEWEB)
Evans, Harold G [Indiana University; Kostelecky, V Alan [Indiana University; Musser, James A [Indiana University
2013-07-29
The elementary particle physics research program at Indiana University spans a broad range of the most interesting topics in this fundamental field, including important contributions to each of the frontiers identified in the recent report of HEPAP's Particle Physics Prioritization Panel: the Energy Frontier, the Intensity Frontier, and the Cosmic Frontier. Experimentally, we contribute to knowledge at the Energy Frontier through our work on the D0 and ATLAS collaborations. We work at the Intensity Frontier on the MINOS and NOvA experiments and participate in R&D for LBNE. We are also very active on the theoretical side of each of these areas with internationally recognized efforts in phenomenology both in and beyond the Standard Model and in lattice QCD. Finally, although not part of this grant, members of the Indiana University particle physics group have strong involvement in several astrophysics projects at the Cosmic Frontier. Our research efforts are divided into three task areas. The Task A group works on D0 and ATLAS; Task B is our theory group; and Task C contains our MINOS, NOvA, and LBNE (LArTPC) research. Each task includes contributions from faculty, senior scientists, postdocs, graduate and undergraduate students, engineers, technicians, and administrative personnel. This work was supported by DOE Grant DE-FG02-91ER40661. In the following, we describe progress made in the research of each task during the final period of the grant, from November 1, 2009 to April 30, 2013.
Studies in theoretical particle physics. Progress report, 1990--1991
Energy Technology Data Exchange (ETDEWEB)
Kaplan, D.B.
1991-07-01
This proposal focuses on research on three distinct areas of particle physics: (1) Nonperturbative QCD. I tend to continue work on analytic modelling of nonperturbative effects in the strong interactions. I have been investigating the theoretical connection between the nonrelativistic quark model and QCD. The primary motivation has been to understand the experimental observation of nonzero matrix elements involving current strange quarks in ordinary matter -- which in the quark model has no strange quark component. This has led to my present work on understanding constituent (quark model) quarks as collective excitations of QCD degrees of freedom. (2) Weak Scale Baryogenesis. A continuation of work on baryogenesis in the early universe from weak interactions. In particular, an investigation of baryogenesis occurring during the weak phase transition through anomalous baryon violating processes in the standard model of weak interactions. (3) Flavor and Compositeness. Further investigation of a new mechanism that I recently discovered for dynamical mass generation for fermions, which naturally leads to a family hierarchy structure. A discussion of recent past work is found in the next section, followed by an outline of the proposed research. A recent publication from each of these three areas is attached to this proposal.
Structural, vibrational and theoretical studies of L-histidine bromide
Ahmed, A. Ben; Feki, H.; Abid, Y.; Boughzala, H.; Mlayah, A.
2008-10-01
This paper presents the results of our calculations of the geometric parameters, vibrational spectra and hyperpolarizability of a non linear optical material, L-histidine bromide. Due to the lack of sufficiently precise information on the geometric structure available in literature, theoretical calculations were preceded by re-determination of the crystal X-ray structure. Single crystals of L-histidine bromide have been grown by slow evaporation of an aqueous solution at room temperature. The compound crystallizes in the non-Centro symmetric space group P2 12 12 1 of the orthorhombic system. Raman spectra have been recorded in the range [200-3500 cm -1]. All observed vibrational bands have been discussed and assigned to normal mode or to combinations and overtones on the basis of our calculations. The optimized geometric bond lengths and bond angles obtained by using HF and DFT (B3LYP and BLYP) show good agreement with the experimental data. Comparison between the measured and the calculated vibrational frequencies indicate that B3LYP is superior to the scaled HF approach for molecular vibrational problems. To investigate microscopic second order non linear optical properties of L-histidine bromide, the electric dipole μ, the polarizability α and the hyperpolarizability β were computed using DFT//B3LYP/6-31G(d) method. According to our calculations, the title compound exhibits non-zero β value revealing microscopic second order NLO behaviour.
Theoretical study of excitation energy transfer in DNA photolyase.
Zheng, Xuehe; Garcia, Jorge; Stuchebrukhov, Alexei A
2008-07-24
Photolyase (PL) is a DNA repair enzyme which splits UV light-induced thymine dimers on DNA by an electron transfer reaction occurring between the photoactivated FADH(-) cofactor and the DNA dimer in the DNA/PL complex. The crystal structure of the DNA/photolyase complex from Anacystis nidulans has been solved. Here, using the experimental crystal structure, we re-examine the details of the repair electron transfer reaction and address the question of energy transfer from the antenna HDF to the redox active FADH(-) cofactor. The photoactivation of FADH(-) immediately preceding the electron transfer is a key step in the repair mechanism that is largely left unexamined theoretically. An important butterfly thermal motion of flavin is identified in ab initio calculations; we propose its role in the back electron transfer from DNA to photolyase. Molecular dynamics simulation of the whole protein/DNA complex is carried out to obtain relevant cofactor conformations for ZINDO/S spectroscopic absorption and fluorescence calculations. We find that significant thermal broadening of the spectral lines, due to protein dynamics, as well as the alignment of the donor HDF and the acceptor FADH(-) transition dipole moments both contribute to the efficiency of energy transfer. The geometric factor of Förster's dipolar coupling is calculated to be 1.82, a large increase from the experimentally estimated 0.67. Using Förster's mechanism, we find that the energy transfer occurs with remarkable efficiency, comparable with the experimentally determined value of 98%.
Theoretical and Computational Studies of Three-dimensional Phase Separation
Wang, K. G.
2005-03-01
The diffusive interactions occurring within a population of precipitates dispersed throughout a contiguous matrix may be described on the basis of a diffusion screening length. Screening theory predicts as functions of the dispersoid volume fraction the changes in diffusion screening length, maximum particle size, coarsening rate, and the scaled particle-size distribution. Furthermore, by considering fluctuations observed in the growth rates of individual particles, we report on developments of a stochastic theory of phase separation. Also, particle-size distributions and the maximum particle radii predicted as a function of time from theory and simulations are shown to agree well with experimental results obtained from measurements performed on Al3Li precipitates in binary Al-Li alloys. Lastly, we calculated the spatial correlation function of these microstructures. We revealed through data analysis the relationship between the critical length scale for diffusion-mediated coarsening and spatial correlations in the microstructure.
Directory of Open Access Journals (Sweden)
Andras Jakab
Full Text Available Attempts to explicate the neural abnormalities behind autism spectrum disorders frequently revealed impaired brain connectivity, yet our knowledge is limited about the alterations linked with autistic traits in the non-clinical population. In our study, we aimed at exploring the neural correlates of dimensional autistic traits using a dual approach of diffusion tensor imaging (DTI and graph theoretical analysis of resting state functional MRI data. Subjects were sampled from a public neuroimaging dataset of healthy volunteers. Inclusion criteria were adult age (age: 18-65, availability of DTI and resting state functional acquisitions and psychological evaluation including the Social Responsiveness Scale (SRS and Autistic Spectrum Screening Questionnaire (ASSQ. The final subject cohort consisted of 127 neurotypicals. Global brain network structure was described by graph theoretical parameters: global and average local efficiency. Regional topology was characterized by degree and efficiency. We provided measurements for diffusion anisotropy. The association between autistic traits and the neuroimaging findings was studied using a general linear model analysis, controlling for the effects of age, gender and IQ profile. Significant negative correlation was found between the degree and efficiency of the right posterior cingulate cortex and autistic traits, measured by the combination of ASSQ and SRS scores. Autistic phenotype was associated with the decrease of whole-brain local efficiency. Reduction of diffusion anisotropy was found bilaterally in the temporal fusiform and parahippocampal gyri. Numerous models describe the autistic brain connectome to be dominated by reduced long-range connections and excessive short-range fibers. Our finding of decreased efficiency supports this hypothesis although the only prominent effect was seen in the posterior limbic lobe, which is known to act as a connector hub. The neural correlates of the autistic trait
Theoretical study on wettability of graphene/water interface
Ishimoto, Takayoshi
2015-12-01
We analyzed the interaction energy between water clusters and graphene model compound by using density functional theory. The mono- and multi-layer interaction of water on graphene models are regarded as the low and high contact angles, which correspond to the wettability of interface, respectively. We clearly found the size dependency of water molecules on graphene model compound for the wettability.
Theoretical Studies of Chemical Reactions following Electronic Excitation
Chaban, Galina M.
2003-01-01
The use of multi-configurational wave functions is demonstrated for several processes: tautomerization reactions in the ground and excited states of the DNA base adenine, dissociation of glycine molecule after electronic excitation, and decomposition/deformation of novel rare gas molecules HRgF. These processes involve bond brealung/formation and require multi-configurational approaches that include dynamic correlation.
A theoretical study on 2-amino-5-nitroprydinium trifluoroaceta
Arioǧlu, ćaǧla; Tamer, Ömer; Başoǧlu, Adil; Avci, Davut; Atalay, Yusuf
2016-03-01
The geometry optimization of 2-amino-5-nitroprydinium trifluoroacetate molecule was carried out by using Becke's three-parameter exchange functional in conjunction with the Lee-Yang-Parr correlation functional (B3LYP) level of density functional theory (DFT) and 6-311++G(d,p) basis set at GAUSSIAN 09 program. The vibration spectrum of the title compound was simulated to predict the presence of functional groups and their vibrational modes. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were calculated at the same level, and the obtained small energy gap shows that charge transfer occurs in the title compound. The molecular dipole moment, polarizability and hyperpolarizability parameters were determined to evaluate nonlinear optical efficiency of the title compound. Finally, the 13C and 1H Nuclear Magnetic Resonance (NMR) chemical shift values were calculated by the application of the gauge independent atomic orbital (GIAO) method. All of the calculations were carried out by using GAUSSIAN 09 program.
Yu, Donghai; Rong, Chunying; Lu, Tian; Chattaraj, Pratim K; De Proft, Frank; Liu, Shubin
2017-07-19
Even though the concept of aromaticity and antiaromaticity is extremely important and widely used, there still exist lots of controversies in the literature, which are believed to be originated from the fact that there are so many aromatic types discovered and at the same time there are many aromaticity indexes proposed. In this work, using seven series of substituted fulvene derivatives as an example and with the information-theoretic approach in density functional reactivity theory, we examine these concepts from a different perspective. We investigate the changing patterns of Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy, information gain, Onicescu information energy, and relative Renyi entropy on the ring carbon atoms of these systems. Meanwhile, we also consider variation trends of four representative kinds of aromaticity indexes such as FLU, HOMA, ASE and NICS. Statistical analyses among these quantities show that with the same ring structure of the derivatives, both information-theoretic quantities and aromaticity indexes obey the same changing pattern, which are valid across all seven systems studied. However, cross correlations between these two sets of quantities yield two completely opposite patterns. These ring-structure dependent correlations are in good agreement with Hückel's 4n + 2 rule of aromaticity and 4n rule of antiaromaticity. Our results should provide a novel and complementary viewpoint on how aromaticity and antiaromaticity should be appreciated and categorized. More studies are in progress to further our understanding about the matter.
A quantum theoretical study of reactions of methyldiazonium ion with DNA base pairs
Energy Technology Data Exchange (ETDEWEB)
Shukla, P.K. [Department of Physics, Assam University, Silchar 788 011 (India); Ganapathy, Vinay [Department of Physics, Banaras Hindu University, Varanasi 221 005 (India); Mishra, P.C., E-mail: pcmishra_in@yahoo.com [Department of Physics, Banaras Hindu University, Varanasi 221 005 (India)
2011-09-22
Graphical abstract: Reactions of methyldiazonium ion at the different sites of the DNA bases in the Watson-Crick GC and AT base pairs were investigated employing density functional and second order Moller-Plesset (MP2) perturbation theories. Display Omitted Highlights: {yields} Methylation of the DNA bases is important as it can cause mutation and cancer. {yields} Methylation reactions of the GC and AT base pairs with CH{sub 3}N{sub 2}{sup +} were not studied earlier theoretically. {yields} Experimental observations have been explained using theoretical methods. - Abstract: Methylation of the DNA bases in the Watson-Crick GC and AT base pairs by the methyldiazonium ion was investigated employing density functional and second order Moller-Plesset (MP2) perturbation theories. Methylation at the N3, N7 and O6 sites of guanine, N1, N3 and N7 sites of adenine, O2 and N3 sites of cytosine and the O2 and O4 sites of thymine were considered. The computed reactivities for methylation follow the order N7(guanine) > N3(adenine) > O6(guanine) which is in agreement with experiment. The base pairing in DNA is found to play a significant role with regard to reactivities of the different sites.
THEORETICAL AND METHODOLOGICAL BASIS OF THE STUDY OF ENVIRONMENTAL AUDIT IN KAZAKHSTAN
Directory of Open Access Journals (Sweden)
V. Berezuyuk
2014-12-01
Full Text Available Practical problems of modern economic development of the country are associated with unresolved major theoretical issues in the field of auditing. One of them, in our opinion, is to determine the status of the audit as a form of scientific knowledge. This, in turn, requires a clear definition of the subject of audit, missing not only in domestic but also foreign economic literature. Theoretical study of the content and scope of the audit showed that there are different interpretations of this concept in the countries with developed market economies (US, UK and the Kazakhstan legislation. Analysis of multiple interpretations and definitions revealed a narrow view of the audit activities in Kazakhstan legislation. In order to improve the efficiency of the audit work is recommended management of large and medium-sized organizations use simulation methods, structural analysis and design based on the Conditional Split of the company business processes, sub-processes, procedures, functions, etc., which, ultimately, will allow Sort already performed the action and determine the need for the implementation of new procedures or functions aimed at improving the quality of the audit. Each audit organization yourself looking for ways to improve the quality of solutions using a variety of techniques, using the experience and creating in-house auditing standards, in particular, for the effective planning of the audit.
Opto-electronic properties of Ta3N5: a joint experimental and theoretical study
Morbec, Juliana; Rocca, Dario; Pinaud, Blaise; Jaramillo, Thomas; Galli, Giulia
2014-03-01
Tantalum nitride (Ta3N5) is considered a promising material for use in photoelectrochemical cells, due to its suitable band gap for visible light absorption and favorable band-edge positions for water splitting. However, Ta3N5 films have been recently shown to exhibit low photocurrent (i.e. less than 50% of the theoretical limit). We report a joint experimental and ab initio theoretical study of the opto-electronic properties of Ta3N5, aimed at understanding possible reasons for the limited photocurrent. Our experimental optical spectra of films with different thicknesses show two absorption edges at 2.1 and 2.5 eV. To provide an interpretation of these features, we performed ab initio calculations, at several levels of theory, of the electronic band structure and optical absorption spectra of Ta3N5. We employed density functional theory with semi-local (PBE/LDA) and hybrid (PBE0/HSE06) functionals and many body perturbation theory at the G0W0 level, and we obtained optical spectra by solving the Bethe-Salpeter equation within density matrix perturbation theory. Work supported by DOE/BES DE-FG02-06ER46262 and NSF-CHE-1305124. Computing resources are partially provided by NERSC.
Theoretical Studies of Dielectronic Recombination of Aluminum-Like Ions
Gorczyca, Tom; Abdel Naby, S. A.; Nikolic, D.; Badnell, N. R.; Savin, D. W.
2008-05-01
Dielectronic recombination (DR) is an important process occurring in astrophysical plasmas. DR is responsible for the charge state balance as well as the cooling of astrophysical plasmas, and it is the dominant electron-ion recombination process in both photoionized and collisionally-ionized plasmas. Accurate and reliable calculations for DR rate coefficients are needed to analyze the spectra obtained from astrophysical observations. Over the past few years, our group has computed reliable DR data for all isoelectronic sequences up through Mg-like ions using a state-of-the-art multiconfiguration Breit-Pauli (MCBP) distorted wave method. Recently, we have focused our work on the complex third-row M-shell isoelectronic sequences, especially Al-like. Although there exist some DR calculations for S IV, those were performed only within a non-relativistic LS-coupling approximation and for higher temperatures more suitable for collisionally-ionized plasmas but not for the lower temperatures appropriate for photoionized plasmas. Fe XIV DR calculations have been completed and tested against the Heidelberg heavy-ion Test Storage Ring facility measurements. MCBP cross sections and rate coefficients of a wide range of Al-like ions, computed using the AUTOSTRUCTURE suite of atomic structure and collision codes, will be presented. The effect of fine structure splitting in the ground state will be discussed, and comparisons against all available data, theoretical as well as experimental, will be shown. Our results are fitted into a simple formula for easier implementation into modeling codes used by the astrophysics community. This work was funded in part by NASA (APRA), NASA (SHP) SR&T, and UK PPARC grants.
Experimental and theoretical studies of a pyrazole-thiazolidin-2,4-di-one hybrid
Mushtaque, Md.; Avecilla, Fernando; Haque, Ashanul; Perwez, Ahmad; Khan, Md. Shahzad; Rizvi, M. Moshahid Alam
2017-08-01
The present work describes synthesis, characterization and biological evaluations of a hybrid compound 10 composed of two intriguing scaffolds pyrazole and thiazolidin-2,4-di-one. The title compound was obtained via multi-step reaction and characterized by a number of techniques (viz. IR, UV-Visible, 1H-NMR, 13C-NMR and MS) including X-ray crystallography. The structural and photophysical data of compound 10 were well supported by theoretical calculations performed at density functional (DFT) level. In-vitro anticancer studies on different human cancer cell lines indicated moderate to low activity of the compounds. The molecular target of the compound was predicted through in-silico studies. Finding of the studies are presented herein.
Fonseca, Matheus C.; Nascimento, Clebio S.; Borges, Keyller B.
2016-02-01
The purpose of this Letter was to study for the first time the interaction process of tramadol (TRM) with distinct functional monomers (FM) in the formation of molecular imprinted polymer (MIP), using density functional theory (DFT) calculations at B3LYP/6-31G(d,p). As result we were able to establish that the best MIP synthesis conditions are obtained with acrylic acid as FM in 1:3 molar ratio and with chloroform as solvent. This condition presented the lowest stabilization energy for the pre-polymerization complexes. Besides, the intermolecular hydrogen bonds found between the template molecule and functional monomers play a primary role to the complex stability.
Directory of Open Access Journals (Sweden)
T. N. Mishchenko
2014-10-01
- Hopf equation using the correlation method of factorization. Practical value. The developed method and the technique that is based on it, allow predicting electric traction loadings of the traction network, as well as the other devices of the traction energy systems and the electric motive power in the different modes of operation and, in particular, during the high-speed train traffic. The method takes into account the load influence (and its mode of operation of the adjacent feeder zones on the electromagnetic processes in the studied inter-substation area. Thus, it is important that the required voltages and currents are considered as the random functions.
A Theoretical and Experimental Study of DNA Self-assembly
Chandran, Harish
The control of matter and phenomena at the nanoscale is fast becoming one of the most important challenges of the 21st century with wide-ranging applications from energy and health care to computing and material science. Conventional top-down approaches to nanotechnology, having served us well for long, are reaching their inherent limitations. Meanwhile, bottom-up methods such as self-assembly are emerging as viable alternatives for nanoscale fabrication and manipulation. A particularly successful bottom up technique is DNA self-assembly where a set of carefully designed DNA strands form a nanoscale object as a consequence of specific, local interactions among the different components, without external direction. The final product of the self-assembly process might be a static nanostructure or a dynamic nanodevice that performs a specific function. Over the past two decades, DNA self-assembly has produced stunning nanoscale objects such as 2D and 3D lattices, polyhedra and addressable arbitrary shaped substrates, and a myriad of nanoscale devices such as molecular tweezers, computational circuits, biosensors and molecular assembly lines. In this dissertation we study multiple problems in the theory, simulations and experiments of DNA self-assembly. We extend the Turing-universal mathematical framework of self-assembly known as the Tile Assembly Model by incorporating randomization during the assembly process. This allows us to reduce the tile complexity of linear assemblies. We develop multiple techniques to build linear assemblies of expected length N using far fewer tile types than previously possible. We abstract the fundamental properties of DNA and develop a biochemical system, which we call meta-DNA, based entirely on strands of DNA as the only component molecule. We further develop various enzyme-free protocols to manipulate meta-DNA systems and provide strand level details along with abstract notations for these mechanisms. We simulate DNA circuits by
Directory of Open Access Journals (Sweden)
Michael Mananghaya
2012-01-01
Full Text Available An important technique to increase the solubility and reactivity of carbon nanotube is through functionalization. In this study, the effects of functionalization of some single-walled carbon nanotubes (SWCNTs were investigated with the aid of density functional theory. The SWCNT model used in the study consists of a finite, (5, 0 zigzag nanotube segment containing 60 C atoms with hydrogen atoms added to the dangling bonds of the perimeter carbons. There are three water-dispersible SWCNTs used in this study that were functionalized with (a formic acid, as a model of carboxylic acid, (b isophthalic acid, as a model aromatic dicarboxylic acid, and (c benzenesulfonic acid, as a model aromatic sulfonic acid. Binding energies of the organic radicals to the nanotubes are calculated, as well as the HOMO-LUMO gaps and dipole moments of both nanotubes and functionalized nanotubes. Binding was found out to be thermodynamically favorable. The functionalization increases the electrical dipole moments and results in an enhancement in the solubility of the nanotubes in water manifested through favorable changes in the free energies of solvation. This should lower the toxicity of nanotubes and improve their biocompatibility.
Theoretical study of precision and accuracy of strain analysis by nano-beam electron diffraction
Energy Technology Data Exchange (ETDEWEB)
Mahr, Christoph, E-mail: mahr@ifp.uni-bremen.de; Müller-Caspary, Knut; Grieb, Tim; Schowalter, Marco; Mehrtens, Thorsten; Krause, Florian F.; Zillmann, Dennis; Rosenauer, Andreas
2015-11-15
Measurement of lattice strain is important to characterize semiconductor nanostructures. As strain has large influence on the electronic band structure, methods for the measurement of strain with high precision, accuracy and spatial resolution in a large field of view are mandatory. In this paper we present a theoretical study of precision and accuracy of measurement of strain by convergent nano-beam electron diffraction. It is found that the accuracy of the evaluation suffers from halos in the diffraction pattern caused by a variation of strain within the area covered by the focussed electron beam. This effect, which is expected to be strong at sharp interfaces between materials with different lattice plane distances, will be discussed for convergent-beam electron diffraction patterns using a conventional probe and for patterns formed by a precessing electron beam. Furthermore, we discuss approaches to optimize the accuracy of strain measured at interfaces. The study is based on the evaluation of diffraction patterns simulated for different realistic structures that have been investigated experimentally in former publications. These simulations account for thermal diffuse scattering using the frozen-lattice approach and the modulation-transfer function of the image-recording system. The influence of Poisson noise is also investigated. - Highlights: • Theoretical study of precision and accuracy of strain analysis by nano-beam electron diffraction. • Evaluation of simulations for exact knowledge of the actual strain. • Improvement of precision using electron beam precession. • Explanation of artefacts in the measurement close to interfaces. • Theoretical solution for the improvement of the accuracy at interfaces.
Theoretical Studies of the Relaxation Matrix for Molecular Systems
Ma, Qiancheng; Boulet, C.
2016-06-01
The phenomenon of collisional transfer of intensity due to line mixing has an increasing importance for atmospheric monitoring. From a theoretical point of view, all relevant information about the collisional processes is contained in the relaxation matrix where the diagonal elements give half-widths and shifts, and the off-diagonal elements correspond to line interferences. For simple systems such as those consisting of diatom-atom or diatom-diatom, accurate fully quantum calculations based on interaction potentials are feasible. However, fully quantum calculations become unrealistic for more complex systems. On the other hand, the semi-classical Robert-Bonamy formalism, which has been widely used to calculate half-widths and shifts for decades, fails in calculating the off-diagonal matrix elements resulting from applying the isolated line approximation. As a result, in order to simulate atmospheric spectra where the effects from line mixing are important, semi-empirical fitting or scaling laws such as the energy corrected sudden (ECS) and the infinite order sudden (IOS) models are commonly used. Recently, we have found that in developing this semi-classical line shape theory, to rely on the isolated line approximation is not necessary. By eliminating this unjustified assumption, and accurately evaluating matrix elements of the exponential operators, we have developed a more capable formalism that enables one not only to reduce uncertainties for calculated half-widths and shifts, but also to calculate the whole relaxation matrix. This implies that we can address the line mixing with the semi-classical theory based on interaction potentials between molecular absorber and molecular perturber. We have applied this formalism for Raman and infrared spectra of linear and asymmetric-top molecules. Recently, the method has been extended into symmetric-tops with inverse symmetry such as the NH3 molecule. Our calculated half-widths of NH3 lines in the νb{1} and the pure
Theoretical Studies of Spectroscopic Line Mixing in Remote Sensing Applications
Ma, Q.; Boulet, C.; Tipping, R. H.
2015-01-01
The phenomenon of collisional transfer of intensity due to line mixing has an increasing importance for atmospheric monitoring. From a theoretical point of view, all relevant information about the collisional processes is contained in the relaxation matrix where the diagonal elements give half-widths and shifts, and the off-diagonal elements correspond to line interferences. For simple systems such as those consisting of diatom-atom or diatom-diatom, accurate fully quantum calculations based on interaction potentials are feasible. However, fully quantum calculations become unrealistic for more complex systems. On the other hand, the semi-classical Robert-Bonamy (RB) formalism, which has been widely used to calculate half-widths and shifts for decades, fails in calculating the off-diagonal matrix elements. As a result, in order to simulate atmospheric spectra where the effects from line mixing are important, semi-empirical fitting or scaling laws such as the ECS (Energy-Corrected Sudden) and IOS (Infinite-Order Sudden) models are commonly used. Recently, while scrutinizing the development of the RB formalism, we have found that these authors applied the isolated line approximation in their evaluating matrix elements of the Liouville scattering operator given in exponential form. Since the criterion of this assumption is so stringent, it is not valid for many systems of interest in atmospheric applications. Furthermore, it is this assumption that blocks the possibility to calculate the whole relaxation matrix at all. By eliminating this unjustified application, and accurately evaluating matrix elements of the exponential operators, we have developed a more capable formalism. With this new formalism, we are now able not only to reduce uncertainties for calculated half-widths and shifts, but also to remove a once insurmountable obstacle to calculate the whole relaxation matrix. This implies that we can address the line mixing with the semi-classical theory based on
The Study of Pragmatic Vagueness from Adaptation-Theoretic Perspective
Institute of Scientific and Technical Information of China (English)
问栗榕
2013-01-01
Vague language, as an intrinsic nature of human language, is an universal phenomenon in our daily life. Pragmatic vagueness,the actual use of vague language in communication,is often used to reach certain purposes.This paper will mainly dis⁃cuss the nature, deep mechanism and functions of pragmatic vagueness from the linguistic adaptation theory. Finally,the author points out that vagueness expressions are produced as a result of adaption to the certain contexts in order to ensure smooth com⁃munication.
A theoretical study of carbohydrates as corrosion inhibitors of iron
Energy Technology Data Exchange (ETDEWEB)
Khalil, Salim M.; Ali, Nozha M. [Libyan Academy for Graduate Studies, Tripoli (Libyan Arab Jamahiriya). Chemistry Dept.; Ali-Shattle, Elbashir E. [Tripoli Univ. (Libyan Arab Jamahiriya). Chemistry Dept.
2013-08-15
The inhibitive effect of fructose, glucose, lactose, maltose, and sucrose against the iron corrosion is investigated using density functional theory at the B3LYP/6-31 G level (d) to search the relation between the molecular structure and corrosion inhibition. The electronic properties such as the energy of the highest occupied molecular orbital (HOMO), the energy of lowest unoccupied orbital (LUMO), the energy gap (LUMO-HOMO), quantum chemical parameters such as hardness, softness, the fraction of the electron transferred, and the electrophilicity index are reported. The inhibition efficiency of the investigated carbohydrates follows the trend: maltose < sucrose < lactose < fructose < glucose. (orig.)
Theoretical study of aromaticity in inorganic tetramer clusters
Indian Academy of Sciences (India)
Sandeep Nigam; Chiranjib Majumder; S K Kulshreshtha
2006-11-01
Ground state geometry and electronic structure of M$^{2-}_{4}$ cluster (M = B, Al, Ga) have been investigated to evaluate their aromatic properties. The calculations are performed by employing the Density Functional Theory (DFT) method. It is found that all these three clusters adopt square planar configuration. Results reveal that square planar M$^{2-}_{4}$ dianion exhibits characteristics of multifold aromaticity with two delocalised -electrons. In spite of the unstable nature of these dianionic clusters in the gas phase, their interaction with the sodium atoms forms very stable dipyramidal M4Na2 complexes while maintaining their square planar structure and aromaticity.
Varbanov, Hristo P; Jakupec, Michael A; Roller, Alexander; Jensen, Frank; Galanski, Markus; Keppler, Bernhard K
2013-01-10
Octahedral platinum(IV) complexes are promising candidates in the fight against cancer. In order to rationalize the further development of this class of compounds, detailed studies on their mechanisms of action, toxicity, and resistance must be provided and structure-activity relationships must be drawn. Herein, we report on theoretical and QSAR investigations of a series of 53 novel bis-, tris-, and tetrakis(carboxylato)platinum(IV) complexes, synthesized and tested for cytotoxicity in our laboratories. The hybrid DFT functional wb97x was used for optimization of the structure geometry and calculation of the descriptors. Reliable and robust QSAR models with good explanatory and predictive properties were obtained for both the cisplatin sensitive cell line CH1 and the intrinsically cisplatin resistant cell line SW480, with a set of four descriptors.
2012-01-01
Octahedral platinum(IV) complexes are promising candidates in the fight against cancer. In order to rationalize the further development of this class of compounds, detailed studies on their mechanisms of action, toxicity, and resistance must be provided and structure–activity relationships must be drawn. Herein, we report on theoretical and QSAR investigations of a series of 53 novel bis-, tris-, and tetrakis(carboxylato)platinum(IV) complexes, synthesized and tested for cytotoxicity in our laboratories. The hybrid DFT functional wb97x was used for optimization of the structure geometry and calculation of the descriptors. Reliable and robust QSAR models with good explanatory and predictive properties were obtained for both the cisplatin sensitive cell line CH1 and the intrinsically cisplatin resistant cell line SW480, with a set of four descriptors. PMID:23214999
A theoretical study of the elastic and thermal properties of ScRu compound under pressure
Huang, Shuo; Li, Rui-Zi; Qi, San-Tao; Chen, Bao; Shen, Jiang
2014-06-01
The elastic and thermal properties of ScRu under pressure are studied using a first-principles pseudopotential method within the generalized gradient approximation. The calculated lattice parameter and formation enthalpy are in good agreement with the previous experimental and theoretical results. From the static finite strain technique, we obtained three independent elastic constants (C 11, C 12 and C 44) and various secondary elasticity parameters such as shear modulus, Young’s modulus and elastic anisotropy, as functions of pressure. This study also provided the pressure and temperature variations of the bulk modulus, Debye temperature, thermal expansion coefficient and heat capacity in wide pressure (0-60 GPa) and temperature (0-1800 K) ranges.
A theoretical study on the B3 phases of ZnSe: Structural and electronic properties
Indian Academy of Sciences (India)
KHOIROM KABITA; B INDRAJIT SHARMA
2017-07-01
A theoretical study on the structural stability and electronic properties of ZnSe is performed using the localized density approximation (LDA), generalized gradient approximation (GGA) and modified Becke– Johnson (mBJ)with Purdew–Burke–Ernzerhof (PBE-GGA) as the exchange correlation potential using full potentiallinearized augmented plane-wave method of density functional theory (DFT). The electronic structure calculation using the three approximations show that the LDA and the GGA methods underestimated the band gap while the band gap predicted by the mBJ is closer to the experimental result. The mBJ-GGA calculation shows a direct band-gap semiconductor of 2.5 eV. The total and partial densities of states of ZnSe are determined to study the energy band diagram.
A theoretical study on the B3 phases of ZnSe: Structural and electronic properties
Kabita, Khoirom; Sharma, B. Indrajit
2017-07-01
A theoretical study on the structural stability and electronic properties of ZnSe is performed using the localized density approximation (LDA), generalized gradient approximation (GGA) and modified Becke-Johnson (mBJ) with Purdew-Burke-Ernzerhof (PBE-GGA) as the exchange correlation potential using full potential linearized augmented plane-wave method of density functional theory (DFT). The electronic structure calculation using the three approximations show that the LDA and the GGA methods underestimated the band gap while the band gap predicted by the mBJ is closer to the experimental result. The mBJ-GGA calculation shows a direct band-gap semiconductor of 2.5 eV. The total and partial densities of states of ZnSe are determined to study the energy band diagram.
Theoretical and Experimental Study of LiBH4-LiCl Solid Solution
Directory of Open Access Journals (Sweden)
Torben R. Jensen
2012-03-01
Full Text Available Anion substitution is at present one of the pathways to destabilize metal borohydrides for solid state hydrogen storage. In this work, a solid solution of LiBH4 and LiCl is studied by density functional theory (DFT calculations, thermodynamic modeling, X-ray diffraction, and infrared spectroscopy. It is shown that Cl substitution has minor effects on thermodynamic stability of either the orthorhombic or the hexagonal phase of LiBH4. The transformation into the orthorhombic phase in LiBH4 shortly after annealing with LiCl is for the first time followed by infrared measurements. Our findings are in a good agreement with an experimental study of the LiBH4-LiCl solid solution structure and dynamics. This demonstrates the validity of the adopted combined theoretical (DFT calculations and experimental (vibrational spectroscopy approach, to investigate the solid solution formation of complex hydrides.
Barrera, Manuel; Suarez-Llorens, Alfonso; Casas-Ruiz, Melquiades; Alonso, José J.; Vidal, Juan
2017-05-01
A generic theoretical methodology for the calculation of the efficiency of gamma spectrometry systems is introduced in this work. The procedure is valid for any type of source and detector and can be applied to determine the full energy peak and the total efficiency of any source-detector system. The methodology is based on the idea of underlying probability of detection, which describes the physical model for the detection of the gamma radiation at the particular studied situation. This probability depends explicitly on the direction of the gamma radiation, allowing the use of this dependence the development of more realistic and complex models than the traditional models based on the point source integration. The probability function that has to be employed in practice must reproduce the relevant characteristics of the detection process occurring at the particular studied situation. Once the probability is defined, the efficiency calculations can be performed in general by using numerical methods. Monte Carlo integration procedure is especially useful to perform the calculations when complex probability functions are used. The methodology can be used for the direct determination of the efficiency and also for the calculation of corrections that require this determination of the efficiency, as it is the case of coincidence summing, geometric or self-attenuation corrections. In particular, we have applied the procedure to obtain some of the classical self-attenuation correction factors usually employed to correct for the sample attenuation of cylindrical geometry sources. The methodology clarifies the theoretical basis and approximations associated to each factor, by making explicit the probability which is generally hidden and implicit to each model. It has been shown that most of these self-attenuation correction factors can be derived by using a common underlying probability, having this probability a growing level of complexity as it reproduces more precisely
Quantum theoretical study of hydrogen under high pressure
Biermann, S
2001-01-01
In the first chapter we will review our knowledge of the phase diagram of hydrogen. Chapter 2 is a summary of the standard density functional and molecular dynamics methods and shows how these are combined in the Car-Parrinello method. Here the nuclei are still treated as classical particles obeying Newtonian mechanics. In chapter 3 we drop this approximation. The path integral description of quantum statistics is added on top of the classical Car-Parrinello method and yields a formalism that includes quantum effects due to the finite de Broglie wavelength of the nuclei. Some technical aspects, namely the parallel implementation of the Path Integral Car-Parrinello (PICP) method, are discussed in chapter 4. In chapter 5 we present the results of our PICP calculations and compare them with prior calculations using the classical Car-Parrinello method as described in chapter 2.
Theoretical Studies on the Interactions of Cations with Diazine
Institute of Scientific and Technical Information of China (English)
CHEN Xing; WU Wen-Peng; ZHANG Jing-Lai; CAO Ze-Xing
2006-01-01
Density functional theory and MP2 calculations have been used to determine the geometries, stabilities, binding energies, and dissociative properties of cation-diazine complexes Mn+-C4H4N2 (Mn+ = Li+, B+, Al+, Be2+, Mg2+, Ca2+). The calculated results indicate that most complexes are stable except the π complexes of Ca2+-pyridazine, Ca2+-pyrazine, Al+-pyrimidine and Al+-pyrimidine. The σ complexes are generally much more stable than their π counterparts. Among the π complexes, the cation-pyrazine π complexes have slightly higher stability. The nature of the ion-molecule interactions has been discussed by the natural bond orbital analysis and frontier molecular orbital interactions. In these σ complexes, there is stronger covalent interaction between B+ and diazine. In the selected π complexes, B+ and Be2+ have stronger covalent interaction with diazine, while the other cations mainly have electrostatic interaction with diazine.
Substituent effects of iron porphyrins: Structural, kinetic, and theoretical studies
Energy Technology Data Exchange (ETDEWEB)
Lu Xiaoquan, E-mail: luxq@nwnu.edu.c [Key Laboratory of Bioelectrochemistry and Environmental Analysis of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, 730070 (China); Ma Junying; Sun Ruiping; Nan Mina; Meng Fanfu; Du Jie; Wang Xiaoyan; Shang Hui [Key Laboratory of Bioelectrochemistry and Environmental Analysis of Gansu Province, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou, 730070 (China)
2010-12-15
Substituent effects of iron porphyrin complexes on the structures and kinetic processes have been examined for the first time. Basing on the premise that iron porphyrin is functional analogous to heme, a series of iron porphyrin derivatives bearing different substituents at the meso positions of the corrole ring are investigated as to their electrochemistry, the relationships among the electron transfer (ET) processes, their structures, and orbital energies. The good coherence between the experiment and theory indicates that the ET rate can be accelerated when electron-donating substituents are introduced to the iron porphyrin ring. Finally, the implications of the results are discussed in the influence of stability of iron porphyrin complexes on the ability to carry molecular oxygen, which may suggest it possible to dominate the biological activity of heme by selecting the appropriate substituents to iron porphyrin ring.
Theoretical Study of Some Nitrososulfamide Compounds with Antitumor Activity
Directory of Open Access Journals (Sweden)
Madi Fatiha
2004-09-01
Full Text Available The lowest-energy conformations of four 2-chloroethylnitrososulfamides were determined using the MM+ molecular mechanics method as implemented in Hyperchem 6.0. Some of the calculated structural parameters, angles and bonds lengths were compared with the crystal structure data of N-nitroso-N-(2-chloroethyl-NÃ¢Â€Â™-sulfamoyl- proline. Using MM+, AM1 and PM3 the anti conformation was predicted to be more stable than the syn conformation in each of these compounds. With these methods we found that the relative energy of the transition state (TS was considerably higher, but with the ab initio method using RHF with minimal basic function STO-3G we found that the syn conformation is predicted to be slightly more stable. The determination of some atomic charges of a selection of atoms on the syn, anti and TS structures of the various compounds provided some details about the nature of the transition state.
Theoretical Studies on the Isomerizations of CH3NO2
Institute of Scientific and Technical Information of China (English)
YANG Lijuan; LI Xiaoyan; ZENG Yanli; MENG Lingpeng; ZHENG Shijun
2009-01-01
The isomerizations of CH3NO2 (NM) have been investigated by density function theory (DFT) and electron density topological analysis methods. Nine isomers and eight isomerization channels were found. The connection relationship between the transition state (TS) and the isomers was confirmed by intrinsic reaction coordinate (IRC) tracing calculation. The calculation results show that in the CH3NO2→CH3ONOt process, the TS is a tight one (CH3NO2 does not break into CH3 and NO2 throughout the reaction), which is consistent with Arenass' results. A long structure transition region, which contains a four-numbered ring → a five-numbered ring → a four-numbered ring → a five-numbered ring structure, exists in CH3NOOc→CH2NOOH process. And it is the first time that a five-numbered ring TS was found in reaction.
Theoretical study on thermal decomposition of azoisobutyronitrile in ground state
Institute of Scientific and Technical Information of China (English)
SUN Chengke; ZHAO Hongmei; LI Zonghe
2004-01-01
The thermal decomposition mechanisms of azoisobutyronitrile (AIBN) in the ground state have been investigated systematically. Based on the potential energy surfaces (PES) of various possible dissociation paths obtained using the semiempirical AM1 method with partial optimization, the density function theory B3LYP/6-311G* method was employed to optimize the geometric parameters of the reactants, the intermediates, the products and the transition states,which were further confirmed by the vibrational analysis. The obtained results show that the reaction process of the two-bond (three-body) simultaneous cleavage Me2(CN)C-N=Nleading to the reaction proceeding in the former pathway. The calculation results were consistent with all the experimental facts.
Adhesion at WC/diamond interfaces - A theoretical study
Padmanabhan, Haricharan; Rao, M. S. Ramachandra; Nanda, B. R. K.
2015-06-01
We investigate the adhesion at the interface of face-centered tungsten-carbide (001) and diamond (001) from density-functional calculations. Four high-symmetry model interfaces, representing different lattice orientations for either side of the interface, are constructed to incorporate different degrees of strain arising due to lattice mismatch. The adhesion, estimated from the ideal work of separation, is found to be in the range of 4 - 7 J m-2 and is comparable to that of metal-carbide interfaces. Maximum adhesion occurs when WC and diamond slabs have the same orientation, even though such a growth induces large epitaxial strain at the interface. From electronic structure calculations, we attribute the adhesion to covalent interaction between carbon p-orbitals as well as partial ionic interaction between the tungsten d- and carbon p-orbitals across the interface.
Adhesion at WC/diamond interfaces - A theoretical study
Energy Technology Data Exchange (ETDEWEB)
Padmanabhan, Haricharan [Department of Engineering Design, Indian Institute of Technology Madras, Chennai – 600036 (India); Rao, M. S. Ramachandra [Department of Physics and Nano-Functional Materials Technology Centre, Indian Institute of Technology Madras, Chennai – 600036 (India); Nanda, B. R. K., E-mail: nandab@iitm.ac.in [Department of Physics, Indian Institute of Technology Madras, Chennai – 600036 (India)
2015-06-24
We investigate the adhesion at the interface of face-centered tungsten-carbide (001) and diamond (001) from density-functional calculations. Four high-symmetry model interfaces, representing different lattice orientations for either side of the interface, are constructed to incorporate different degrees of strain arising due to lattice mismatch. The adhesion, estimated from the ideal work of separation, is found to be in the range of 4 - 7 J m{sup −2} and is comparable to that of metal-carbide interfaces. Maximum adhesion occurs when WC and diamond slabs have the same orientation, even though such a growth induces large epitaxial strain at the interface. From electronic structure calculations, we attribute the adhesion to covalent interaction between carbon p-orbitals as well as partial ionic interaction between the tungsten d- and carbon p-orbitals across the interface.
Metal Ion Selectivity of Kojate Complexes: A Theoretical Study
Directory of Open Access Journals (Sweden)
Sarita Singh
2013-01-01
Full Text Available Density functional calculations have been performed on four-coordinate kojate complexes of selected divalent metal ions in order to determine the affinity of the metal ions for the kojate ion. The complexation reactions are characterized by high energies, showing that they are highly exothermic. It is found that Ni(II exhibits the highest affinity for the kojate ion, and this is attributed to the largest amount of charge transfer from the ligand to the metal ion. The Ni(II complex has distorted square planar structure. The HOMOs and LUMOs of the complexes are also discussed. All complexes display a strong band at ~1500 cm−1 corresponding to the stretching frequency of the weakened carbonyl bond. Comparison of the complexation energies for the two steps shows that most of the complexation energy is realized in the first step. The energy released in the second step is about one-third that of the first step.
Nekoei, A-R; Vakili, M; Hakimi-Tabar, M; Tayyari, S F; Afzali, R; Kjaergaard, H G
2014-07-15
There are some discrepancies in both the vibrational assignments and in the metal-ligand (M-L) bond strengths predicted in the previous studies on the copper (II) chelated complex of dibenzoylmethane, Cu(dbm)2. Also, there is a lack of theoretical structure, Raman spectrum and full vibrational assignment for Cu(dbm)2 in the literatures. Density functional theory (DFT) at the B3LYP level and also MP2 calculations using different basis sets, besides Natural Bond Orbital (NBO) and Atoms-in-Molecules (AIM) analyses, have been employed to investigate the effect of methyl substitution with the phenyl group on the stabilities of bis(acetylacetonate) copper (II), Cu(acac)2, and Cu(dbm)2 complexes and the electron delocalization in their chelated rings. Measured solid phase infrared and Raman bands for Cu(dbm)2 complex have been interpreted in terms of the calculated vibrational modes and detailed assignment has been presented. We concluded that, theoretically, the results of charge transfer studies, and experimentally, in-phase symmetric O-Cu-O stretching mode of these complexes are very useful measures for M-L bond strength. The electron delocalization in the chelated rings and the M-L bond strength in Cu(dbm)2 are concluded to be higher than those in Cu(acac)2. The calculated geometries and vibrational results are in good agreement with the experimental data.
Bending of the calmodulin central helix : A theoretical study
VanderSpoel, D; DeGroot, BL; Hayward, S; Berendsen, HJC; Vogel, HJ
1996-01-01
The crystal structure of calcium-calmodulin (CaM) reveals a protein with a typical dumbbell structure. Various spectroscopic studies have suggested that the central linker region of CaM, which is alpha-helical in the crystal structure, is flexible in solution. In particular, NMR studies have indicat
Theoretical studies of non inductive current drive in compact toroids
Farengo, R; Lifschitz, AF; Caputi, KI; Arista, NR; Clemente, RA
2002-01-01
Three non inductive current drive methods that can be applied to compact toroids axe studied. The use of neutral beams to drive current in field reversed configurations and spheromaks is studied using a Monte Carlo code that includes a complete ionization package and follows the exact particle orbit
Freezing of bentonite. Experimental studies and theoretical considerations
Energy Technology Data Exchange (ETDEWEB)
Birgersson, Martin; Karnland, Ola; Nilsson, Ulf (Clay Technology AB, Lund (Sweden))
2010-01-15
During its lifetime, a KBS-3 repository will be subject to various ambient temperatures. Backfilled tunnels, shafts and investigation bore holes closest to ground level will experience periods of temperature below 0 deg C. From a safety assessment perspective, it is therefore essential to understand the behavior of compacted bentonite below 0 deg C. A theoretical framework for predicting the pressure response in compacted water saturated bentonite due to temperature changes has been developed based on thermodynamics and a single pore-type. This model predicts an approximately linear temperature dependence of swelling pressure P{sub s}(w,DELTAT) = P{sub s}(w,0 deg C) + DELTAs(w)DELTAT/nu{sub clay}(w) where DELTAT denotes a temperature difference from 0 deg C, DELTAs(w) is the difference in partial molar entropy between clay water and bulk water, nu{sub clay} (w) is the partial molar volume of the clay water and w denotes the water/solid mass ratio of the clay. As bulk water changes phase at 0 deg C, DELTAs(w) has a different value dependent on whether DELTAT is negative or positive. Above 0 deg C DELTAs(w) is a small value for all relevant densities which means that the pressure response due to temperature changes is small. A further consequence of this fact is that DELTAs(w) is a large positive number below 0 deg C when the external water phase is transformed to ice. Consequently, the model predicts a large drop of swelling pressure with temperature below 0 deg C, in the order of 1.2 MPa/deg C. Specifically, the swelling pressure is zero at a certain (negative) temperature T{sub C}. T{sub C} also quantifies the freezing point of the bentonite sample under consideration, as ice formation in the bentonite does not occur until swelling pressure is lost. A large set of laboratory tests have been performed where fully water saturated samples of bentonites have been exposed to temperatures in the range -10 deg C to +25 deg C. The swelling pressure response has been
Freezing of bentonite. Experimental studies and theoretical considerations
Energy Technology Data Exchange (ETDEWEB)
Birgersson, Martin; Karnland, Ola; Nilsson, Ulf (Clay Technology AB, Lund (Sweden))
2010-01-15
During its lifetime, a KBS-3 repository will be subject to various ambient temperatures. Backfilled tunnels, shafts and investigation bore holes closest to ground level will experience periods of temperature below 0 deg C. From a safety assessment perspective, it is therefore essential to understand the behavior of compacted bentonite below 0 deg C. A theoretical framework for predicting the pressure response in compacted water saturated bentonite due to temperature changes has been developed based on thermodynamics and a single pore-type. This model predicts an approximately linear temperature dependence of swelling pressure P{sub s}(w,DELTAT) = P{sub s}(w,0 deg C) + DELTAs(w)DELTAT/nu{sub clay}(w) where DELTAT denotes a temperature difference from 0 deg C, DELTAs(w) is the difference in partial molar entropy between clay water and bulk water, nu{sub clay} (w) is the partial molar volume of the clay water and w denotes the water/solid mass ratio of the clay. As bulk water changes phase at 0 deg C, DELTAs(w) has a different value dependent on whether DELTAT is negative or positive. Above 0 deg C DELTAs(w) is a small value for all relevant densities which means that the pressure response due to temperature changes is small. A further consequence of this fact is that DELTAs(w) is a large positive number below 0 deg C when the external water phase is transformed to ice. Consequently, the model predicts a large drop of swelling pressure with temperature below 0 deg C, in the order of 1.2 MPa/deg C. Specifically, the swelling pressure is zero at a certain (negative) temperature T{sub C}. T{sub C} also quantifies the freezing point of the bentonite sample under consideration, as ice formation in the bentonite does not occur until swelling pressure is lost. A large set of laboratory tests have been performed where fully water saturated samples of bentonites have been exposed to temperatures in the range -10 deg C to +25 deg C. The swelling pressure response has been
Theoretical and Experimental Studies of Magneto-Rayleigh-Taylor Instabilities
Energy Technology Data Exchange (ETDEWEB)
Lau, Yue Ying [University of Michigan, Ann Arbor, MI (United States); Gilgenbach, Ronald [University of Michigan, Ann Arbor, MI (United States)
2013-07-07
Magneto-Rayleigh-Taylor instability (MRT) is important to magnetized target fusion, wire-array z-pinches, and equation-of-state studies using flyer plates or isentropic compression. It is also important to the study of the crab nebula. The investigators performed MRT experiments on thin foils, driven by the mega-ampere linear transformer driver (LTD) facility completed in their laboratory. This is the first 1-MA LTD in the USA. Initial experiments on the seeding of MRT were performed. Also completed was an analytic study of MRT for a finite plasma slab with arbitrary magnetic fields tangential to the interfaces. The effects of magnetic shear and feedthrough were analyzed.
Experimental and Theoretical Studies of Pressure Broadened Alkali-Metal Atom Resonance Lines
Shindo, F.; Zhu, C.; Kirby, K.; Babb, J. F.
2006-01-01
We are carrying out a joint theoretical and experimental research program to study the broadening of alkali atom resonance lines due to collisions with helium and molecular hydrogen for applications to spectroscopic studies of brown dwarfs and extrasolar giant planets.
theoretical study of physiochemical properties of insulin-like growth ...
African Journals Online (AJOL)
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Monte Carlo, Molecular Dynamics and Langevin simulation methods by MM+, AMBER and. OPLS force fields of ... This study has demonstrated that the simple model, which includes an ...... solubility of perfluorobenzene in the supercritical ...
Gestsdottir, Steinunn; Lewin-Bizan, Selva; von Eye, Alexander; Lerner, Jacqueline V.; Lerner, Richard M.
2009-01-01
Intentional self-regulation is a core facet of human functioning, involving people's modulation of their thoughts, attention, emotions, and behaviors to react to environmental demands and to influence their own development. Using data from Grades 8, 9, and 10 of the 4-H Study of Positive Youth Development (PYD), the structure of intentional…
Sample correlations of infinite variance time series models: an empirical and theoretical study
Directory of Open Access Journals (Sweden)
Jason Cohen
1998-01-01
Full Text Available When the elements of a stationary ergodic time series have finite variance the sample correlation function converges (with probability 1 to the theoretical correlation function. What happens in the case where the variance is infinite? In certain cases, the sample correlation function converges in probability to a constant, but not always. If within a class of heavy tailed time series the sample correlation functions do not converge to a constant, then more care must be taken in making inferences and in model selection on the basis of sample autocorrelations. We experimented with simulating various heavy tailed stationary sequences in an attempt to understand what causes the sample correlation function to converge or not to converge to a constant. In two new cases, namely the sum of two independent moving averages and a random permutation scheme, we are able to provide theoretical explanations for a random limit of the sample autocorrelation function as the sample grows.
Shiroudi, Abolfazl; Deleuze, Michael S
2014-05-22
Reaction mechanisms for the initial stages of naphthalene oxidation at high temperatures (T ≥ 600 K) have been studied theoretically using density functional theory along with various exchange-correlation functionals, as well as the benchmark CBS-QB3 quantum chemical approach. These stages correspond to the removal of hydrogen atoms by hydroxyl radical and the formation thereby of 1- and 2-naphthyl radicals. Bimolecular kinetic rate constants were estimated by means of transition state theory. The excellent agreement with the available experimental kinetic rate constants demonstrates that a two-step reaction scheme prevails. Comparison with results obtained with density functional theory in conjunction with various exchange-correlation functionals also shows that DFT remains unsuited for quantitative insights into kinetic rate constants. Analysis of the computed structures, bond orders, and free energy profiles demonstrates that the reaction steps involved in the removal of hydrogen atoms by OH radicals satisfy Hammond's principle. Computations of branching ratios also show that these reactions do not exhibit a particularly pronounced site-selectivity.
Theoretical study of cathode surfaces and high-temperature superconductors
Mueller, Wolfgang
1995-01-01
Calculations are presented for the work functions of BaO on W, Os, Pt, and alloys of Re-W, Os-W, and Ir-W that are in excellent agreement with experiment. The observed emission enhancement for alloy relative to tungsten dispenser cathodes is attributed to properties of the substrate crystal structure and explained by the smaller depolarization of the surface dipole on hexagonal as compared to cubic substrates. For Ba and BaO on W(100), the geometry of the adsorbates has been determined by a comparison of inverse photoemission spectra with calculated densities of unoccupied states based on the fully relativistic embedded cluster approach. Results are also discussed for models of scandate cathodes and the electronic structure of oxygen on W(100) at room and elevated temperatures. A detailed comparison is made for the surface electronic structure of the high-temperature superconductor YBa2Cu3O7 as obtained with non-, quasi-, and fully relativistic cluster calculations.
Radical-cationic gaseous amino acids: a theoretical study.
Sutherland, Kailee N; Mineau, Philippe C; Orlova, Galina
2007-08-16
Three major forms of gaseous radical-cationic amino acids (RCAAs), keto (COOH), enolic (C(OH)OH), and zwitterionic (COO(-)), as well as their tautomers, are examined for aliphatic Ala(.+), Pro(.+), and Ser(.+), sulfur-containing Cys(.+), aromatic Trp(.+), Tyr(.+), and Phe(.+), and basic His(.+). The hybrid B3LYP exchange-correlation functional with various basis sets along with the highly correlated CCSD(T) method is used. For all RCAAs considered, the main stabilizing factor is spin delocalization; for His(.+), protonation of the basic side chain is equally important. Minor stabilizing factors are hydrogen bonding and 3e-2c interactions. An efficient spin delocalization along the N-C(alpha)-C(O-)O moiety occurs upon H-transfer from C(alpha) to the carboxylic group to yield the captodative enolic form, which is the lowest-energy isomer for Ala(.+), Pro(.+), Ser(.+), Cys(.+), Tyr(.+), and Phe(.+). This H-transfer occurs in a single step as a 1,3-shift through the sigma-system. For His(.+), the lowest-energy isomer is formed upon H-transfer from C(alpha) to the basic side chain, which results in a keto form, with spin delocalized along the N-C(alpha)-C=O fragment. Trp(.+) is the only RCAA that favors spin delocalization over an aromatic system given the low ionization energy of indole. The lowest-energy isomer of Trp(.+) is a keto form, with no H-transfer.
Amphiphilic organic ion pairs in solution: a theoretical study.
Pradines, Vincent; Poteau, Romuald; Pimienta, Veronique
2007-07-16
The macroscopic manifestation of hydrophobic interactions for amphiphilic organic ion pairs (tetraalkylammonium-anion) has been shown experimentally by measuring their association constants and their affinity with the organic phase. Beyond a certain size, there is a direct relation between association constants and chain lengths in tetraalkylammonium ions. We propose to cast a bridge between these results and geometrical properties considered at the level of a single ion pair by means of quantum chemistry calculations performed on model systems: trimethylalkylammonium-pentyl sulfate instead of tetraalkylammonium-dodecyl sulfate. Two limiting cases are considered: head-to-head configurations, which yield an optimal electrostatic interaction between polar heads, and parallel configurations with a balance between electrostatic and hydrophobic interactions. All properties (geometries, complexation energies, and atomic charges) were obtained at the MP2 level of calculation, with water described by a continuum model (CPCM). Dispersion forces link hydrocarbon chains of tetraalkylammonium ions and pentyl sulfate, thus yielding (for the largest ion pairs) parallel configurations favored with respect to head-to-head geometries by solute-solvent electrostatic interactions. Given the small experimental association energies, we probe the accuracy limit of the MP2 and CPCM methods. However, clear trends are obtained as a function of chain length, which agree with the experimental observations. The calculated monotonic stabilization of ion pairs when the hydrocarbon chain increases in length is discussed in terms of electrostatic interactions (between ions and between ion pairs and water), dispersion forces, and cavitation energies.
New free radicals to measure antiradical capacity: a theoretical study.
León-Carmona, Jorge Rafael; Martínez, Ana; Galano, Annia
2014-08-28
A new family of free radicals, that are soluble in water and stable at all pH values, were recently synthesized and used to assess the antiradical capacity of several polyphenols. In the present work, density functional calculations were used to investigate the single electron transfer reactions between these new free radicals and polyphenols in aqueous solution. The quantification of the antiradical capacity is a challenge, particularly for polyphenols, since they become unstable under experimental conditions. It was found that the electron transfer from polyphenols to the newly developed free radicals can be used to assess the efficiency of this kind of compound for preventing oxidative stress. Since one of the free radicals can be deprotonated under experimental conditions, this newly synthesized radical can help distinguish more clearly between different antiradical compounds with similar antioxidant capacity by modifying the pH in the experiments. The results reported here are in good agreement with the available experimental data and allowed making recommendations about possible experimental conditions in the design of antioxidant assays using the investigated radicals.
Theoretical study for Bond between Reinforcement steel and Concrete
Directory of Open Access Journals (Sweden)
usama mostafa mahran
2013-04-01
Full Text Available The behavior and load carrying behavior of reinforced concrete structures is influence by the interaction between the concrete and reinforcement. The stress transfer between reinforcement and concrete in the longitudinal direction of the bars is called bond. An essential feature of reinforced concrete is the bond between steel and concrete. Anchorage of reinforcement depends on the bond between steel and concrete, crack width and crack spacing are mainly governed by it. So, stiffness, deformation and dynamic behavior are influenced by it, and in reverse loading damping and energy dissipation is a function of bond. This is one of the reasons why bond has been, and still is, a topic of fundamental and applied research. Bond stress is the equivalent unit shear stress acting in parallel to the reinforcing bar on the interface between reinforcing steel bar and concrete. Due to the transfer of forces through bond stress, between the reinforcing rebar and concrete, the force in the reinforcing bar changes along its length. Because bond stress is thought of as stress per unit area of bar surface, it is related to the rate of change of steel stress. Consequently, to have bond stress it is necessary to have a changing steel stress. In cases of high stress at the contact interface, near cracks or end anchorages, the bond stresses are related to relative displacements between concrete and steel. These relative displacements, which are caused by different average strains in the concrete and the steel, are usually called bond-slip (t-d.
Experimental and Theoretical Studies in Hydrogen-Bonding Organocatalysis
Directory of Open Access Journals (Sweden)
Matej Žabka
2015-08-01
Full Text Available Chiral thioureas and squaramides are among the most prominent hydrogen-bond bifunctional organocatalysts now extensively used for various transformations, including aldol, Michael, Mannich and Diels-Alder reactions. More importantly, the experimental and computational study of the mode of activation has begun to attract considerable attention. Various experimental, spectroscopic and calculation methods are now frequently used, often as an integrated approach, to establish the reaction mechanism, the mode of activation or explain the stereochemical outcome of the reaction. This article comprises several case studies, sorted according to the method used in their study. The aim of this review is to give the investigators an overview of the methods currently utilized for mechanistic investigations in hydrogen-bonding organocatalysis.
Theoretical Studies on N2H+O Reaction
Institute of Scientific and Technical Information of China (English)
L(U) Ying-wen; L(U) Wen-cai; SU Zhong-min
2008-01-01
The N2H+O potential energy profile was studied at the CCSD(T)/6-311G++(dfp)//MP2/6-311G(d,p) level.Reactions associated with four intermediates(cis-HNNO, trans-HNNO, NNHO, and NNOH) were investigated. The results indicate that N2H+O reaction toward H+N2O is more favored than that toward N2+OH, consistent with previous experimental studies. The pathways for the two reactions are found to go through cis-HNNO, transition state, and finally to the products. The N2H+O→NH+NO reaction was studied in detail. Product NO in such a reaction is likely to occur via cis-HNNO, followed by trans-HNNO, and finally dissociates into NH+NO. These results suggest that N2H+O→NH+NO is an important channel in NO production.
TEBPP: Theoretical and Experimental study of Beam-Plasma-Physics
Anderson, H. R.; Bernstein, W.; Linson, L. M.; Papadopoulos, K.; Kellogg, P. J.; Szuszczewicz, E. P.; Hallinan, T. J.; Leinbach, H.
1980-01-01
The interaction of an electron beam (0 to 10 keV, 0 to 1.5 Amp) with the plasma and neutral atmospheres at 200 to 400 km altitude is studied with emphasis on applications to near Earth and cosmical plasmas. The interaction occurs in four space time regions: (1) near electron gun, beam coming into equilibrium with medium; (2) equilibrium propagation in ionosphere; (3) ahead of beam pulse, temporal and spatial precursors; (4) behind a beam pulse. While region 2 is of the greatest interest, it is essential to study Region 1 because it determines the characteristics of the beam as it enters 2 through 4.
Theoretical study of reaction mechanism for NCO + HCNO
Zhang, Weichao; Du, Benni; Feng, Changjun
2007-07-01
A detailed quantum chemical study is performed on the mechanism of the NCO + HCNO reaction, which has never been studied by theory. The potential energy surface for this reaction is characterized at the B3LYP/6-311++G(d,p) level of theory, combined with high-level CBS-QB3 single point energy calculation. Four possible product channels have been investigated. From the calculations it can be seen that the formation of HCN + NO + CO is the dominant product channel, while the pathway to products of HCNN + CO 2 is expected to be minor one, and these conclusions are in good agreement with the experimental results.
Generation, structure and reactivity of arynes: A theoretical study
Indian Academy of Sciences (India)
Peter G S Dkhar; R H Duncan Lyngdoh
2000-04-01
The semiempirical AM1 SCF-MO method is used to study the benzyne mechanism for aromatic nucleophilic substitution of various -substituted chlorobenzenes and 3-chloropyridine. The calculations predict that most of the fixed substituents studied here would induce the formation of 2,3-arynes through their electron-withdrawing resonance or inductive effects. The geometry and electronic structure of the 2,3- and 3,4-arynes investigated here, confirm the generally accepted -benzyne structure postulated for arynes. The sites of nucleophilic addition to arynes as predicted here are in fair agreement with expectation and experimental findings.
Is it really theoretical? A review of sampling in grounded theory studies in nursing journals.
McCrae, Niall; Purssell, Edward
2016-10-01
Grounded theory is a distinct method of qualitative research, where core features are theoretical sampling and constant comparative analysis. However, inconsistent application of these activities has been observed in published studies. This review assessed the use of theoretical sampling in grounded theory studies in nursing journals. An adapted systematic review was conducted. Three leading nursing journals (2010-2014) were searched for studies stating grounded theory as the method. Sampling was assessed using a concise rating tool. A high proportion (86%) of the 134 articles described an iterative process of data collection and analysis. However, half of the studies did not demonstrate theoretical sampling, with many studies declaring or indicating a purposive sampling approach throughout. Specific reporting guidelines for grounded theory studies should be developed to ensure that study reports describe an iterative process of fieldwork and theoretical development. © 2016 John Wiley & Sons Ltd.
Band gap opening in graphene: a short theoretical study
Sahu, Sivabrata; Rout, G. C.
2017-03-01
Graphene, being a gapless semiconductor, cannot be used in pristine form for nano-electronic applications. Therefore, it is essential to generate a finite gap in the energy dispersion at Dirac point. We present here the tight-binding model Hamiltonian taking into account of various interactions for tuning band gap in graphene. The model Hamiltonian describes the hopping of the π-electrons up to third nearest-neighbours, substrate effects, Coulomb interaction at two sub-lattices, electron-phonon interaction in graphene-on-substrates and high phonon frequency vibrations, besides the bi-layer graphene. We have solved the Hamiltonian using Zubarev's double time single particle Green's function technique. The quasi-particle energies, electron band dispersions, the expression for effective band gap and the density of states (DOS) are calculated numerically. The results are discussed by varying different model parameters of the system. It is observed that the electron DOS and band dispersion exhibit linear energy dependence near Dirac point for nearest-neighbour hopping integral. However, the second and third nearest-neighbour hoppings provide asymmetry in DOS. The band dispersions exhibit wider band gaps with stronger substrate effect. The modified gap in graphene-on-substrate attains its maximum value for Coulomb interaction energy U_{C} = 1.7 t1 . The critical Coulomb interaction is enhanced to U_{C} = 2.5 t1 to produce maximum band gap in the presence of electron-phonon interaction and phonon vibration. The bi-layer graphene exhibits Mexican hat type band gap near Dirac point for transverse gating potential. The other conclusions for the present work are described in the text.
Experimental and theoretical study of 4-formyl pyrrole derived aroylhydrazones
Rawat, Poonam; Singh, R. N.
2015-03-01
Two new 4-formyl pyrrole derived aroylhydrazones (3a, b) from ethyl 4-formyl-3,5-dimetyl-1H-pyrrole-2-carboxylate and aroylhydrazides (3,5-dinitrobenzohydrazide/2-hydrazinocarbonyl-N-phenyl-acetamide) have been synthesized and characterized by various spectroscopic techniques 1H NMR, Mass, UV-Visible and FT-IR. The calculated thermodynamic parameters show that the formation of 3a as spontaneous, whereas 3b as non-spontaneous. TD-DFT has been used to calculate the absorption wavelengths, oscillator strength (f) and the nature of electronic excitations. Natural bond orbital (NBO) analysis has been carried out to explore the various conjugative and hyperconjugative interactions and their second order stabilization energy (E(2)) within monomer and its dimer. The dimer formation of 3a, 3b due to result of intermolecular hydrogen bonding N1sbnd H30⋯O84, N1sbnd H28⋯O60 is obvious in 1H NMR, NBO and FT-IR as down field chemical shifts, n(O84) → σ∗(N1sbnd H30), n(O60) → σ∗(N1sbnd H28) interactions, vibrational red shifts, respectively. To determine the strength and nature of hydrogen bonding, topological parameters at bond critical points (BCP) have been analyzed by 'Quantum theory of Atoms in molecules' (QTAIM) in detail. The global electrophilicity index (ω) has been calculated to determine the relative electrophilic strength of molecules. The local reactivity descriptors analyses such as Fukui functions (fk+, fk-), local softnesses (sk+, sk-) and electrophilicity indices (ωk+, ωk-) have been performed to determine the reactive sites within molecules. The first hyperpolarizabilities (β0) of 3a, b have been computed to evaluate the non-linear optical (NLO) response of the investigated molecules.
Theoretical Study on the Intermolecular Interactions of Tetrazole Dimers
Institute of Scientific and Technical Information of China (English)
无
2005-01-01
Tetrazole monomers (Ⅰ,Ⅱ) and all of their possible stable dimers (1, 2, 3, 4, 5, 6, 7and 8) were fully optimized by DFT method at the B3LYP/6-311++G** level. Among the eight dimers, there were two 1H-tetrazole dimers, three 2H-tetrazole dimers and three hetero dimers of 1H-tetrazole and 2H-tetrazole. Vibrational frequencies were calculated to ascertain that each structure was stable (no imaginary frequencies). The basis set superposition errors (BSSE) are 2.78,2.28, 2.97, 2.75, 2.74, 2.18, 1.23 and 3.10 kJ/mol, and the zero point energy (ZPE) corrections for the interaction energies are 4.88, 4.18, 3.87, 3.65, 3.54, 3.22, 2.87 and 4.34 kJ/mol for 1, 2, 3, 4, 5, 6,7 and 8, respectively. After BSSE and ZPE corrections, the greatest corrected intermolecular interaction energy ofthe dimers is -43.71 kJ/mol. The charge redistribution mainly occurs on the very small. Natural bond orbital (NBO) analysis was performed to reveal the origin of the interaction. Based on the statistical thermodynamic method, the standard thermodynamic functions, heat capacities (C0p), entropies (S0T) and thermal corrections to enthalpy (H0T), and the changes of thermodynamic properties from monomer to dimer in the temperature range of 200.00 K to 700 K have been obtained. 1H-tetrazole monomer can spontaneously tum into two stable dimers at 298.15 K.
Wang, Xiaoyan; Wu, Wei; Ju, Haidong; Zou, Taoyu; Qiao, Zhenfang; Gong, Hao; Wang, Hai
2016-12-01
By using organic vapor phase deposition method, nickel phthalocyanines (NiPc) nanowires were successfully prepared, and the effects of heating temperature on the structural and optical properties of NiPc nanowires were investigated. Both the crystal structures of NiPc powders and nanowires are studied by x-ray diffraction patterns (XRD) and Fourier transform infrared spectra (FTIR). The lattice constants of NiPc nanowires from the fitting of XRD patterns are a = 13.04 Å, b = 3.75 Å, c = 24.32 Å, β = 94.10°, belonging to the space group of monoclinic (P21/c). X-ray photo-electron spectroscopy (XPS) suggests main peaks at 284.82 eV and 286.18 eV for C-C and C-N bonds and two peaks at 397.8 eV and 398.8 eV for N-C and the N-Ni bonds, respectively, in NiPc nanowires. FTIR spectra show a structural transition from powder to nanowire. The optical properties of NiPc nanowires have been investigated via a comparison between theoretical and experimental approaches. The most significant absorption peaks of NiPc nanowires in the visible region are located at 626 nm and 672 nm, showing a blue shift comparing with the β-NiPc. We have also theoretically revealed the excitation energies in NiPc single molecule and dimer in the form of α and β phases using time-dependent density-functional theory. These theoretical results are in qualitative agreement with the measurements of optical properties. Moreover, no noticeable change in crystalline form is shown when tuning the heating temperature from 420 °C to 450 °C, suggesting a wide synthesis temperature window. The reduced Ni-Ni distance indicated a clear advantage over powder in terms of potential applications in organic electronics.
Understanding the equatorial ocean : theoretical and observational studies
Rabitti, A.
2016-01-01
By means of a variety of approaches, the present study points out the challenges in understanding equatorial ocean dynamics (±2.5º). Standard theory, in fact, fails in accurately describing such a big portion of our ocean. This is mainly because at the equator rotation and density stratification com
Theoretical studies of the dynamics of chemical reactions
Energy Technology Data Exchange (ETDEWEB)
Wagner, A.F. [Argonne National Laboratory, IL (United States)
1993-12-01
Recent research effort has focussed on several reactions pertinent to combustion. The formation of the formyl radical from atomic hydrogen and carbon monoxide, recombination of alkyl radicals and halo-alkyl radicals with halogen atoms, and the thermal dissociation of hydrogen cyanide and acetylene have been studied by modeling. In addition, the inelastic collisions of NCO with helium have been investigated.
Theoretical Studies in Chemical Kinetics - Annual Report, 1970.
Karplus, Martin
1970-10-01
The research performed includes (a) Alkali-Halide, Alkali-Halide (MX, M’X’) Exchange Reactions; (b) Inversion Problem; (c) Quantum Mechanics of Scattering Processes, (d) Transition State Analysis of Classical Trajectories, (e) Differential Cross Sections from Classical Trajectories; and (f) Other Studies.
Theoretical studies of gene substitution, geographic variation, and speciation
Energy Technology Data Exchange (ETDEWEB)
Felsenstein, J.
1977-07-31
Brief comments are given on the results of a research program dealing with population genetics of evolutionary processes. The various subjects studied included genetic variation in clines; speciation and disruptive selection; parapatric speciation in clines; macroevolutionary laws in a model ecosystem; migration matrices; lethal allelism; estimation of number of loci in quantitative inheritance; numerical taxonomy methods; and new mutants in Lesch-Nyhan disease.
Cognition in Orienteering: Theoretical Perspectives and Methods of Study.
Ottosson, Torgny
1996-01-01
Almost without exception, published studies on cognition in orienteering have adopted an information processing perspective involving dualism between objective and subjective worlds. An alternative, experiential framework focuses on the orienteer's conception of (or way of experiencing) the task to be accomplished, and on "affordances" (lines of…
Theoretical study of bone sialoprotein in bone biomineralization
CSIR Research Space (South Africa)
Yang, Y
2011-05-01
Full Text Available , highly conserved across several vertebrates, are the proposed active sites. We selected one of these sites, i.e. (Sp) 2 E 8 , where Sp represents a phosphoserine as a model peptide to study the role of BSP. We used molecular dynamics simulations...
A Density Functional Theory Study
Lim, XiaoZhi
2011-12-11
Complexes with pincer ligand moieties have garnered much attention in the past few decades. They have been shown to be highly active catalysts in several known transition metal-catalyzed organic reactions as well as some unprecedented organic transformations. At the same time, the use of computational organometallic chemistry to aid in the understanding of the mechanisms in organometallic catalysis for the development of improved catalysts is on the rise. While it was common in earlier studies to reduce computational cost by truncating donor group substituents on complexes such as tertbutyl or isopropyl groups to hydrogen or methyl groups, recent advancements in the processing capabilities of computer clusters and codes have streamlined the time required for calculations. As the full modeling of complexes become increasingly popular, a commonly overlooked aspect, especially in the case of complexes bearing isopropyl substituents, is the conformational analysis of complexes. Isopropyl groups generate a different conformer with each 120 ° rotation (rotamer), and it has been found that each rotamer typically resides in its own potential energy well in density functional theory studies. As a result, it can be challenging to select the most appropriate structure for a theoretical study, as the adjustment of isopropyl substituents from a higher-energy rotamer to the lowest-energy rotamer usually does not occur during structure optimization. In this report, the influence of the arrangement of isopropyl substituents in pincer complexes on calculated complex structure energies as well as a case study on the mechanism of the isomerization of an iPrPCP-Fe complex is covered. It was found that as many as 324 rotamers can be generated for a single complex, as in the case of an iPrPCP-Ni formato complex, with the energy difference between the global minimum and the highest local minimum being as large as 16.5 kcalmol-1. In the isomerization of a iPrPCP-Fe complex, it was found
Energy Technology Data Exchange (ETDEWEB)
Zhang, Fan; Nemeth, Karoly; Bareño, Javier; Dogan, Fulya; Bloom, Ira D.; Shaw, Leon L.
2016-01-01
The feasibility of synthesizing functionalized h-BN (FBN) via the reaction between molten LiOH and solid h-BN is studied for the first time and its first ever application as an electrode material in Li-ion batteries is evaluated. Density functional theory (DFT) calculations are performed to provide mechanistic understanding of the possible electrochemical reactions derived from the FBN. Various materials characterizations reveal that the melt-solid reaction can lead to exfoliation and functionalization of h-BN simultaneously, while electrochemical analysis proves that the FBN can reversibly store charges through surface redox reactions with good cycle stability and coulombic efficiency. DFT calculations have provided physical insights into the observed electrochemical properties derived from the FBN.
Experimental and theoretical studies of nanoparticles of antiferromagnetic materials
DEFF Research Database (Denmark)
Mørup, Steen; Madsen, Daniel Esmarch; Frandsen, Cathrine
2007-01-01
The magnetic properties of nanoparticles of antiferromagnetic materials are reviewed. The magnetic structure is often similar to the bulk structure, but there are several examples of size-dependent magnetic structures. Owing to the small magnetic moments of antiferromagnetic nanoparticles......, the commonly used analysis of magnetization curves above the superparamagnetic blocking temperature may give erroneous results, because the distribution in magnetic moments and the magnetic anisotropy are not taken into account. We discuss how the magnetic dynamics can be studied by use of magnetization...... nanoparticles is usually negligible, and therefore such particles present a unique possibility to study exchange interactions between magnetic particles. The interactions can have a significant influence on both the magnetic dynamics and the magnetic structure. Nanoparticles can be attached with a common...
Theoretical study on a Miniature Joule-Thomson & Bernoulli Cryocooler
Xiong, L. Y.; Kaiser, G.; Binneberg, A.
2004-11-01
In this paper, a microchannel-based cryocooler consisting of a compressor, a recuperator and a cold heat exchanger has been developed to study the feasibility of cryogenic cooling by the use of Joule-Thomson effect and Bernoulli effect. A set of governing equations including Bernoulli equations and energy equations are introduced and the performance of the cooler is calculated. The influences of some working conditions and structure parameters on the performance of coolers are discussed in details.
The Case Study Approach: Some Theoretical, Methodological and Applied Considerations
2013-06-01
a large manufacturing organisation in Malaysia . An in- depth case study process (specifically a qualitative approach) was used to illustrate the...researcher closely examined four leaders from generally diverse organisations, who had embraced the learning-organisation concept in order to improve...The researchers focused on the context of learning in the workplace , and they investigated the nature of learning and development opportunities that
Relativistic Multichannel Theory: Theoretical Study of C+ Autoionization States
Institute of Scientific and Technical Information of China (English)
XIA Dan; ZHANG Shi-Zhong; PENG Yong-Lun; LI Jia-Ming
2003-01-01
Based on relativistic multichannel theory, the autoionization states of C+ are studied. We calculate all the autoionization states in the energy region of 193900 ~ 231700cm"1, and the results are in good agreement with the experimental data. The energy structure we obtain will be important in the dielectronic recombination processes, which plays a key role in determining the abundance of carbon in a nebula.
Theoretical study of plasma confinement by magnetic multicusp field
Khalzov, Ivan; Forest, Cary
2014-10-01
Plasma confinement in a magnetic multicusp field is studied numerically using both collisional particle-in-cell and isothermal two-fluid MHD codes and tested against the empirical model. The simulation domain is two-dimensional, periodic in one direction and bounded by absorbing boundaries with multicups field in other direction. First, we study the dependence of plasma loss width on plasma parameters and field strength and compare the results with the well-known empirical formula w = 2√{ρeρi } (two hybrid gyro-radius). Our results show that the loss width has the same scaling with magnetic field w ~ 1 / B , but dependence on other plasma parameters does not agree with this formula. Second, we study the plasma flow drive in the cusp region due to electric field applied by discrete electrodes. The electrode positions are optimized for achieving the highest plasma flow. Comparison with available experimental data from Madison Plasma Dynamo Experiment (MPDX) is made. The work is supported by NSF and DoE.
Experimental and theoretical studies on concrete structures with special-shaped shear walls
Directory of Open Access Journals (Sweden)
LIU Jianxin
2014-06-01
Full Text Available On the basis of concept design and staggered shear panels structure,this paper puts forward a new reinforced concrete high rise biuding structure with special-shaped shear walls and presents an experimental study of the seismic performance of the new special-shaped shear walls structure under low reversed cyclic loading using MTS electro hydraulic servo system.Compared with experimental results,a finite element analysis on this special-shaped shear wall structure,which considers the nonlinearity of concrete structure,is found suitable.It shows that the experimental results fairly confirms to the calculated values,which indicates that this new structure has advantages as good architecture function,big effective space,high overall lateral stiffness,fine ductility,advanced seismic behavior,etc..That is,the close r agreement between the theoretical and experimental results indicates the proposed shear wall structure has wide applications.
Theoretical structural and vibrational study of 5-trifluoromethyluracil. A comparison with uracil
Energy Technology Data Exchange (ETDEWEB)
Rudyk, Roxana; Ramos, María E.; Checa, María A.; Brandán, Silvia A. [Cátedra de Química General, Instituto de Química Inorgánica, Facultad de Bioquímica, Química y Farmacia, Universidad Nacional de Tucumán, Ayacucho 471,(4000), San Miguel de Tucumán, Tucum and #x00E1 (Argentina); Chamorro, Eduardo E. [Facultad de Ciencias Exactas, Universidad Andrés Bello, Avda. República 275, 8370146, Santiago (Chile)
2014-10-06
In the present work, a comparative study on the structural and vibrational properties of the 5-trifluoromethyluracil (TFMU) derivative with those corresponding to uracil in gas and aqueous solution phases was performed combining the available H{sup 1}-NMR, C{sup 13}-NMR, F{sup 19}-NMR and FTIR spectra with Density Functional Theory (DFT) calculations. Three stable conformers were theoretically determined in both media by using the hybrid B3LYP/6-31G* method. The solvent effects were simulated by means of the self-consistent reaction field (SCRF) method employing the integral equation formalism variant (IEFPCM). Complete assignments of the vibrational spectra in both phases were performed combining the internal coordinates analysis and the DFT calculations with the Scaled Quantum Mechanics Force Field (SQMFF) methodology. The atomic charges, bond orders, solvation energies, dipole moments, molecular electrostatic potentials and force constants parameters were calculated for the three conformers of TFMU in gas phase and aqueous solution.
DEFF Research Database (Denmark)
Nekoei, A.-R.; Vakili, M.; Hakimi-Tabar, M.
2014-01-01
There are some discrepancies in both the vibrational assignments and in the metal-ligand (M-L) bond strengths predicted in the previous studies on the copper (II) chelated complex of dibenzoylmethane, Cu(dbm)2. Also, there is a lack of theoretical structure, Raman spectrum and full vibrational...... assignment for Cu(dbm)2 in the literatures. Density functional theory (DFT) at the B3LYP level and also MP2 calculations using different basis sets, besides Natural Bond Orbital (NBO) and Atoms-in-Molecules (AIM) analyses, have been employed to investigate the effect of methyl substitution with the phenyl...... group on the stabilities of bis(acetylacetonate) copper (II), Cu(acac)2, and Cu(dbm)2 complexes and the electron delocalization in their chelated rings. Measured solid phase infrared and Raman bands for Cu(dbm)2 complex have been interpreted in terms of the calculated vibrational modes and detailed...
Directory of Open Access Journals (Sweden)
Jana Schiller
2016-05-01
Full Text Available In this work we demonstrate the ability of a multifaceted N,N′-disubstituted urea to selectively recognize fluoride anion (F− among other halides. This additional function is now added to its already reported organocatalytic and organogelator properties. The signaling mechanism relies on the formation of a charge-transfer (CT complex between the urea-based sensor and F¯ in the ground state with a high association constant as demonstrated by absorption and fluorescence spectroscopy. The nature of the hydrogen bonding interaction between the sensor and F¯ was established by 1H-NMR studies and theoretical calculations. Moreover, the recovery of the sensor was achieved by addition of methanol.
Institute of Scientific and Technical Information of China (English)
孙元红; 赵珂; 王传奎; 罗毅; 延云兴; 陶绪堂; 蒋民华
2005-01-01
The nonlinear optical properties of two newly synthesized molecules 9-Ethyl-3-{2-[4-(2-Pyridin-4-yl-vinyl)-phenyl]-vinyl}-9H-carbazole (EPVPC) and 9-Octadecyl-3-{2-[4-(2-Pyridin-4-yl-vinyl)-phenyl]-vinyl}-9H-carbazole (OPVPC)have been studied with hybrid density functional theory (DFT/B3LYP). The generalized few-state model is employed to calculate the two-photon absorption cross sections of the compounds. The theoretical results are in good agreement with the available experimental measurements. It is found that the maximal two-photon absorption (TPA) cross sections of the compounds can be well described by a three-state model. The numerical simulation shows that both compounds have large two-photon absorption (TPA) cross sections and, furthermore, OPVPC displays a little stronger TPA activity than EPVPC in a lower frequency region.
A theoretical study of the stress relaxation in HMX on the picosecond time scale
Long, Yao; Chen, Jun
2015-12-01
The stress relaxation model of β-HMX on the picosecond time scale is studied by a theoretical approach. The relaxation of normal stress is contributed by lattice vibration, and the relaxation of shear stress is contributed by molecular rotation. Based on this model, the energy dissipation rule of the elastic wave and the profile of the shock wave are investigated. We find at low frequency the dissipation rate of the elastic wave is proportional to the power function of frequency, and under high speed shock loading the width of the stress relaxation zone is less than 0.3 μm there is a pressure peak with a height of 14 GPa near the wave front.
Lin, Tao; Liu, Xiaojun; Lou, Zhidong; Hou, Yanbing; Teng, Feng
2014-08-01
The charge injection and transport properties of six organic light-emitting molecules with push-pull structures were studied by theoretical calculations. The ground-state geometries for the neutral, cationic and anionic states were optimized using density functional theory. Subsequently, the ionization potentials and electron affinities were calculated. We computed the reorganization energies and the transfer integrals based on the Marcus electron transfer theory. It was found that in addition to being emitters the six compounds are multifunctional materials being capable of transport for both holes and electrons. Moreover, the double-branched compound DCDPC2 was found to have higher charge injection ability and better balanced charge transport properties than single-branched compounds.
González-Baró, Ana C.; Pis-Diez, Reinaldo; Parajón-Costa, Beatriz S.; Rey, Nicolás A.
2012-01-01
A complete and detailed study of the hydrazone obtained from condensation of antituberculous isoniazid (hydrazide of the isonicotinic acid, INH) and o-vanillin (2-hydroxy-3-methoxybenzaldehyde, o-HVa) is performed. It includes structural and spectroscopic analyses, comparing experimental and theoretical results. The compound was obtained as a chloride of the pyridinic salt (INHOVA +Cl -) but it will be referred as INHOVA for the sake of simplicity. The conformational space was searched and optimized geometries were determined both in gas phase and including solvent effects. Vibrational (IR and Raman), electronic and NMR spectra were registered and assigned with the help of computational methods based on the Density Functional Theory. Isoniazid hydrazones are good candidates for therapeutic agents against tuberculosis with conserved efficiency and lower toxicity and resistance than parent INH.
Theoretical study of miscibility and glass-forming trends in mixtures of polystyrene spheres
Shih, W.-H.; Stroud, D.
1984-01-01
A theoretical study of glass-forming trends and miscibility in mixtures of polystyrene spheres (polyballs) of different diameters, suspended in an aqueous solution, is presented. The polyballs are assumed to be charged and to interact via a Debye-Hueckel screened Coulomb potential. The Helmholtz free energy is calculated from a variational principle based on the Gibbs-Bogoliubov inequality, in which a mixture of hard spheres of different diameters is chosen as the reference system. It is found that when the charges of the two types of polyballs are sufficiently different, the variationally determined ratio of hard-sphere diameters differs substantially, leading to packing difficulties characteristic of glass formation. The experimentally observed range of glass formation corresponds to a ratio of hard-sphere diameters of 0.8 or less. Calculations of the free energy as a function of concentration indicate that the liquid polyball mixture is stable against the phase separation, even for widely different polyball charges.
Emmeche, C
2000-01-01
In this note epistemological problems in general theories about living systems are considered; in particular, the question of hidden connections between different areas of experience, such as folk biology and scientific biology, and hidden connections between central concepts of theoretical biology, such as function, semiosis, closure, and life.
Role of hot electron transport in scintillators: A theoretical study
Energy Technology Data Exchange (ETDEWEB)
Huang, Huihui [SZU-NUS Collaborative Innovation Center for Optoelectronic Science and Technology, Key Lab. of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, College of Optoelectronic Engineering, Shenzhen Univ. (China); Li, Qi [Physical Sciences Division, IBM TJ Watson Research Center, Yorktown Heights, NY (United States); Department of Computer Science, University of Illinois at Urbana-Champaign, Urbana, IL (United States); Lu, Xinfu; Williams, R.T. [Department of Physics, Wake Forest University, Winston Salem, NC (United States); Qian, Yiyang [College of Engineering and Applied Science, Nanjing University (China); Wu, Yuntao [Scintillation Materials Research Center, University of Tennessee, Knoxville, TN (United States)
2016-10-15
Despite recent intensive study on scintillators, several fundamental questions on scintillator properties are still unknown. In this work, we use ab-initio calculations to determine the energy dependent group velocity of the hot electrons from the electronic structures of several typical scintillators. Based on the calculated group velocities and optical phonon frequencies, a Monte-Carlo simulation of hot electron transport in scintillators is carried out to calculate the thermalization time and diffusion range in selected scintillators. Our simulations provide physical insights on a recent trend of improved proportionality and light yield from mixed halide scintillators. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)
Theoretical studies of the reaction e+ e- --> K+ K- gamma
Lesniak, Leonard
2016-01-01
We present studies of the e+ e- --> K+ K- gamma reaction for the e+e- center-of-mass energies close to the phi(1020) meson mass. Different mechanisms leading to the final state are considered. The strong interaction amplitudes of the K+K- pairs in the S-wave are taken into account. In addition, the photon emission in the initial state, the final state radiation effects and all the possible interference terms are included in the transition matrix elements. The K+K- effective mass distributions and the angular dependence of the reaction cross-section are calculated.
THEORETICAL STUDY OF PODOPHYLLOTOXIN AND QUINOLONE ANALOGUES AS ANTITUMOR DRUGS
Institute of Scientific and Technical Information of China (English)
何峰; 戴颖仪; 朱孝峰; 黄爱东; 张翎; 颜少平; 刘宗潮
2002-01-01
Objective: To study the active sites of podophyllotoxin derivatives. Methods: Some podophyllotoxin derivatives were analyzed by quantum and mechanics method. Results: Some information was given according to the calculation results about HOMO and LUMO electron density. The C-4 position is the position for effective modification. The B ring and E ring are important active centers. Conclusion: The hole of positive charge in B ring easily combines with an acceptor within the molecular. Some quinolones with similar electronic construction to podophyllotoxin may have antitumor activity.
Exergy performance of different space heating systems: A theoretical study
DEFF Research Database (Denmark)
Kazanci, Ongun Berk; Shukuya, Masanori; Olesen, Bjarne W.
2016-01-01
Three space heating systems (floor heating with different floor covering resistances, radiator heating with different working temperatures, warm-air heating with and without heat recovery) were compared using a natural gas fired condensing boiler as the heat source. For the floor heating systems......, the effects of floor covering resistance on the whole system performance were studied using two heat sources; a natural gas fired condensing boiler and an air-source heat pump. The heating systems were also compared in terms of auxiliary exergy use for pumps and fans. The low temperature floor heating system...
Keto-enol tautomerism in estrogen hormone. A theoretical study
Jameh-Bozorghi, Saeed; Shirani, Hossein; Ghaempanah, Aram; Ghapanvari, Hamed
2015-01-01
The HF/6-311+G** calculation was used to investigate Keto-Enol tautomerism of Estrogen Hormone. Molecular geometries of keto, enol and transition state of this reaction were optimized and NBO calculations were performed. These calculation results showed that activation energy (Ea) of Keto-Enol tautomerization of Estrogen is 118.65 Kcal mol-1. Energetic study at B3LYP/6-311+G** level of theory revealed that keto tautomer is more stable structure. NBO analysis results have a good agreements with optimized geometries and experimental data.
Theoretical and methodological studies of continuous microbial bioreactors.
Toda, Kiyoshi
2003-08-01
This article reviews most of the author's studies on process development and reactor design for continuous microbial reactions. (1) Enzyme reactions of growing and non-growing microbial cells immobilized in agar gel beads were analyzed pertaining to the effects of external and internal diffusion of substrate on reaction kinetics. (2) Experimental correlations of production rates of beta-fructosidase and acid phosphatase with dilution rate of continuous culture were simulated based on an operon model for enzyme regulation. (3) Population dynamics of an amylase-producing bacteria and their mutant were discussed in relation to enzyme productivity in a continuous culture of spore-forming bacteria. (4) Plasmid mobilization in a mixed population of donor, recipient, and helper cells was investigated in a continuous culture as a model study of accidental release of a genetically modified plasmid into a natural environment. (5) A production rate increase of up to 100-fold was achieved by cell-recycle culturing of continuous acetic acid fermentation using a filter module with a hollow fiber membrane. (6) The feasibility of a continuous surface culture for the biooxidation of organic substances was ascribed to an enhanced oxygen absorption rate in the presence of a microbial film on a liquid surface. (7) Simultaneous separation of inhibitory products using an electrodialysis module during some organic acid fermentations was effective for increasing production in a continuous culture.
A theoretical study of mechanical stability of arteries.
Rachev, Alexander
2009-05-01
This study proposes a mathematical model for studying stability of arteries subjected to a longitudinal extension and a periodic pressure. An artery was considered as a straight composite beam comprised of an external thick-walled tube and a fluid core. The dynamic criterion for stability was used, based on analyzing the small transverse vibrations superposed on the finite deformation of the vessel under static load. In contrast to the case of a static pressurization, in which buckling is only possible if the load produces a critical axial compressive force, a loss of stability of arteries under periodic pressure occurs under many combinations of load parameters. Instability occurs as a parametric resonance characterized by an exponential increase in the amplitude of transverse vibrations over several bands of pressure frequencies. The effects of load parameters were analyzed on the basis of the results for a dynamic and static stability of a rabbit thoracic aorta. Under normal physiological loads the artery is in a stable configuration. Static instability occurs under high distending pressures and low longitudinal stretch ratios. When the artery is subjected to periodic pressure, an independent increase in the mean pressure, amplitude of the periodic pressure, or frequency, most often, but not always, increases the risk of stability loss. In contrary, an increase in longitudinal stretch ratio most likely, but not certain, stabilizes the vessel. It was shown that adaptive geometrical remodeling due to an increase in mean pressure and flow does not affect artery stability.
An in-depth analysis of theoretical frameworks for the study of care coordination1
Van Houdt, Sabine; Heyrman, Jan; Vanhaecht, Kris; Sermeus, Walter; De Lepeleire, Jan
2013-01-01
Introduction Complex chronic conditions often require long-term care from various healthcare professionals. Thus, maintaining quality care requires care coordination. Concepts for the study of care coordination require clarification to develop, study and evaluate coordination strategies. In 2007, the Agency for Healthcare Research and Quality defined care coordination and proposed five theoretical frameworks for exploring care coordination. This study aimed to update current theoretical frame...
An in-depth analysis of theoretical frameworks for the study of care coordination
Sabine Van Houdt; Jan Heyrman; Kris Vanhaecht; Walter Sermeus; Jan De Lepeleire
2013-01-01
Introduction: Complex chronic conditions often require long-term care from various healthcare professionals. Thus, maintaining quality care requires care coordination. Concepts for the study of care coordination require clarification to develop, study and evaluate coordination strategies. In 2007, the Agency for Healthcare Research and Quality defined care coordination and proposed five theoretical frameworks for exploring care coordination. This study aimed to update current theoretical fram...
Theoretical Study of Sodium-Water Surface Reaction Mechanism
Kikuchi, Shin; Kurihara, Akikazu; Ohshima, Hiroyuki; Hashimoto, Kenro
Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using the ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule on the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. It was found that the estimated rate constant of the former was much larger than the latter. The results are the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by Japan Atomic Energy Agency (JAEA) toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR).
Theoretical Studies on Defects of Kaolinite in Clays
Institute of Scientific and Technical Information of China (English)
HE Man-Chao; FANG Zhi-Jie; ZHANG Ping
2009-01-01
Using the first-principles methods, we study the formation energetics and charge doping properties of the extrinsic substitutional defects in kaolinite. Especially, we choose Be, Mg, Ca, Fe, Cr, Mn, Cu, Zn as extrinsic defects to substitute for AI atoms. By systematically calculating the impurity formation energies and transition energy levels, we find that all group-Ⅱ defects introduce the relative shallow transition energy levels in kaolinite. Among them, MgAI has the shallowest transition energy leve! at 0.08 eV above the valence band maximum. The transitionelemental defects ReAl, CrAl and MnAl are found to have relative low formation energies, suggesting their easy formation in kaolinite under natural surrounding conditions. Our calculations show that the defects CuAl and ZnAl have the high formation energies and deep transition energy levels, which exclude the possibility of their formation in natural kaolinite.
Exergy performance of different space heating systems: A theoretical study
DEFF Research Database (Denmark)
Kazanci, Ongun Berk; Shukuya, Masanori; Olesen, Bjarne W.
2016-01-01
Three space heating systems (floor heating with different floor covering resistances, radiator heating with different working temperatures, warm-air heating with and without heat recovery) were compared using a natural gas fired condensing boiler as the heat source. For the floor heating systems......, the effects of floor covering resistance on the whole system performance were studied using two heat sources; a natural gas fired condensing boiler and an air-source heat pump. The heating systems were also compared in terms of auxiliary exergy use for pumps and fans. The low temperature floor heating system...... performed better than other systems in terms of exergy demand. The use of boiler as a heat source for a low-exergy floor heating system creates a mismatch in the exergy supply and demand. Although an air-source heat pump could be a better heat source, this depends on the origin of the electricity supplied...
Experiment and Theoretical Analysis Study of ETFE Inflatable Tubes
Directory of Open Access Journals (Sweden)
YanLi He
2014-01-01
Full Text Available The load bearing capacity of an ETFE (ethylene-tetra-fluoro-ethylene inflatable tube is tested in this paper, and a comparative study of two wrinkling theories, the bifurcation theory and the tension field theory, is carried out for wrinkling analysis of the ETFE inflatable tube. Results obtained from the bifurcation theory and experiment reveal the limitations of tension field theory on the wrinkling analysis. The load-displacement curves of inflatable beams under bending load are obtained and compared with the experimental results; curves obtained using the bifurcation theory show coincidence with experimental curves, but the curves obtained using the tension field theory have noticeable deviations between calculated and experimental results.
Theoretical Study on Ion Escape in Martian Atmosphere
Institute of Scientific and Technical Information of China (English)
SHI Jian-Kui; LIU Zhen-Xing; Klaus TORKAR; Tielong ZHANG
2007-01-01
@@ Based on the observation that Martian magnetic moment is gradually reducing from the ancient to the present,we investigate the O+ ion flux distribution along magnetic field lines and the ion escaping flux in Martian tail with different assumed Martian magnetic moments. The results show that the O+ ion flux along magnetic field lines decreases with distance from Mars; the ion flux along the field line decreases more quickly if the magnetic moment is larger; the larger the magnetic moment, the smaller the ion escaping flux in the Martian tail. The ion escaping flux depends on Z-coordinate in the Martian tail. With decrease of the magnetic moment, the ion escaping flux in the Martian tail increases. The results are significant for studying the water loss from Mars surface.
Experimental and theoretical studies on visible light attenuation in water
Simpson, A; Cho, H J; Liu, H
2014-01-01
In this study we describe lab experiments on determining the above water reflectance Rrs coefficient, and the water attenuation coefficient Kd for fresh water. Different types of screens (totally absorbent, gray, etc.) were submerged in water (0-0.6 m) and illuminated from outside. The spectral density of the water leaving radiance was measured for different depths. The results were ran by a code which took into account the geometry of the incident irradiation, the geometry of the screen under water, and boundary conditions at the water surface provided by the radiation transfer theory. From the experimental data and our model we obtain the spectral distribution of the attenuation coefficient for fresh water and compared it with other data in literature. These experiments, performed in the Nonlinear Wave Lab at ERAU# represent just a preliminary calibration of the experimental protocol. More tests with water of different degrees of turbidity, and possibly wave filed at the water surface are in progress and wi...
Polymers' surface interactions with molten iron: A theoretical study
Assadi, M. Hussein N.; Sahajwalla, Veena
2014-10-01
Environmental concerns are the chief drive for more innovative recycling techniques for end-of-life polymeric products. One attractive option is taking advantage of C and H content of polymeric waste in steelmaking industry. In this work, we examined the interaction of two high production polymers i.e. polyurethane and polysulfide with molten iron using ab initio molecular dynamics simulation. We demonstrate that both polymers can be used as carburizers for molten iron. Additionally, we found that light weight H2 and CHx molecules were released as by-products of the polymer-molten iron interaction. The outcomes of this study will have applications in the carburization of molten iron during ladle metallurgy and waste plastic injection in electric arc furnace.
Theoretical studies of the transport property of oligosilane
Institute of Scientific and Technical Information of China (English)
无
2010-01-01
The transport mechanisms of four-conjugated systems were comparatively studied by combining ATK and Gaussian 03 calculations.It was found that the charge-doped oligosilane behaved in a different way from the boron doped and phosphorus doped oligosilanes in terms of the transmission property.The charge-doped oligosilane showed almost no conductivity owing to the damage of the electron transfer path by charge-doping.By contrast,the boron doped and phosphorus doped oligosilanes were demonstrated to be good semiconductors and NDR behavior was observed for them.This is a reasonable result after the analysis of the transmission spectra,MPSH states,energy gap,conjugation effect,and scattering effect.
A theoretical study of radon measurement with activated charcoal
Nikezić, Dragoslav; Urošević, Vlade
1998-02-01
Diffusion of radon in a bed of activated charcoal is described by diffusion equations. An analytical solution of these equations is presented for the case of constant radon concentration in the atmosphere. The solutions are given separately for short term and long term exposure. An analytical form of the calibration constant f for long term exposure and constant radon concentration in air, was found to be f=kp {D}/{λ}S {sinh{λ}/{D}l }/{cosh{λ}/{D}l } A numerical method and computer code based on the method of finite elements is developed for the case of variable radon concentration in air. This program simulates radon adsorption by the activated charcoal bed, enabling determination of sensitivity. The dependence of sensitivity on different parameters, such as temperature, thickness of the charcoal, etc. was studied using this program.
Theoretical study of hafnium oxide as a gate-material for CMOS devices
Sharia, Onise
The continual downscaling of the thickness of the SiO 2 layer in the complementary metal oxide semiconductor (CMOS) transistors has been one of the main driving forces behind the growth of the semiconductor industry for past 20-30 years. The gate dielectric works as a capacitor and therefore the reduction in thickness results in increase of capacitance and the speed of the device. However, this process has reached the limit when the further reduction of the SiO2 thickness will result in a leakage current above the acceptable limit, especially for mobile devices. This problem can be resolved by replacing SiO2 with materials which have higher dielectric constants (high-k). The leading candidates to replace SiO 2 as a gate material are hafnium dioxide and hafnium silicate. However, several problems arise when using these materials in the device. One of them is to find p and n type gate metals to match with the valence and conduction band edges of silicon. This problem can be rooted in lack of our understanding of the band alignment and its controlling mechanisms between the materials in the gate stack. Theoretical simulations using density functional theory can be very useful to address such problems. In this dissertation present a theoretical study of the band alignment between HfO2 and SiO 2 interface. We identify oxygen coordination as a governing factor for the band alignment. Next, we discuss effects of Al incorporation on the band alignment at the SiO2/HfO2 interface. We find that one can tune the band alignment by controlling the concentration of Al atoms in the stack. We also perform a theoretical study of HfO2/Metal interface in case of Rh. We identify Rh as a good candidate for a p-type gate metal due to its large work-function and the low oxidation energy. Finally, we report a study of the stability of oxygen vacancies across the gate stack. We model a gate stack composed of n-Si/SiO2/HO2/Rh. We find that oxygen vacancies are easier to create in SiO2 than
The theoretical studies of piezoresistive effect in diamond films
Institute of Scientific and Technical Information of China (English)
KONG; Chunyang
2002-01-01
［1］Jiang, X., Schiffmann, K., Klages, C. P., Nucleation and initial growth phase of diamond thin films on(100)silicon, Phys. Rev., 1994, B50(12): 8402-8410.［2］Jiang, X., Klages, C. P., Zachai, R. et al., Epitaxial diamond thin films on(100)silicon substrate, Appl. Phys. Lett., 1993, 62(26): 3438-3440.［3］Deguchi, M., Kitabatake, M., Hirao, T. et al., PR properties of chemical-vapor-deposited p-type diamond strain-gauges fabricared on diaphragm structure, Diamond Relat. Mater., 1996,5: 728-731.［4］Wang, W. L., Liao, K. J., Feng, B. et al., PR of p-type heteroepitaxial diamond films on Si(100), Diamond Relat. Matet., 1998, 7: 528-532.［5］Wang, W. L., Jiang, X., Taube, K. et al., PR of polycrystalline p-type diamond films of various doping levels at different temperatures, J. Appl. Phys., 1997, 82(2): 729-732.［6］Fang, L., Wang, W. L., Ding, P. D. et al., Study on the PR effect of crystalline and polycrystalline diamond under uniaxial strains, J. Appl. Phys., 1999, 86(9): 5185-5193.［7］Fang, L., Wang, W. L., Ding, P. D. et al., Study on the PR effect in p-type polycrystalline diamond, Science in China, 1999, 42(7): 769-778.［8］Aslam, M., Taher, I., Masood, A., Piezoresistivity invapor deposited diamond films, Appl. Phys. Lett., 1992, 60: 2923-2925.［9］Sondheimer, E. H., The mean free path of electrons in metals, Advan. Phys., 1952, 1: 1-42.［10］Fuchs, K., The conductivity of thin metallic films according to the electron theory of metals, Proc. Cambridge Phil. Soc., 1938, 34: 100-108.［11］Xue, Z. Q., Wu, Q. D., Li, J., Physics of Thin Films(in Chinese), 2nd ed., Beijing: Publishing House of Electronics Industry, 1991, 282-284.［12］Beer, A. C., Willardson, R. K., Hall and transverse magnetoresistance effects for warped bands and mixed scattering, Phys. Rev., 1958, 110: 1286-1294.［13］Kenneth, J. R., William, J. L., High-field magnetoresistance of semiconducting diamond, Phys. Rev., 1972, B6: 4588-4592.
Theoretical studies of excited state 1,3 dipolar cycloadditions
Belluccci, Michael A.
The 1,3 dipolar photocycloaddition reaction between 3-hydroxy-4',5,7-trimethoxyflavone (3-HTMF) and methyl cinnamate is investigated in this work. Since its inception in 2004 [JACS, 124, 13260 (2004)], this reaction remains at the forefront in the synthetic design of the rocaglamide natural products. The reaction is multi-faceted in that it involves multiple excited states and is contingent upon excited state intramolecular proton transfer (ESIPT) in 3-HTMF. Given the complexity of the reaction, there remain many questions regarding the underlying mechanism. Consequently, throughout this work we investigate the mechanism of the reaction along with a number of other properties that directly influence it. To investigate the photocycloaddition reaction, we began by studying the effects of different solvent environments on the ESIPT reaction in 3-hydroxyflavone since this underlying reaction is sensitive to the solvent environment and directly influences the cycloaddition. To study the ESIPT reaction, we developed a parallel multi-level genetic program to fit accurate empirical valence bond (EVB) potentials to ab initio data. We found that simulations with our EVB potentials accurately reproduced experimentally determined reaction rates, fluorescence spectra, and vibrational frequency spectra in all solvents. Furthermore, we found that the ultrafast ESIPT process results from a combination of ballistic transfer and intramolecular vibrational redistribution. To investigate the cycloaddition reaction mechanism, we utilized the string method to obtain minimum energy paths on the ab initio potential. These calculations demonstrated that the reaction can proceed through formation of an exciplex in the S1 state, followed by a non-adiabatic transition to the ground state. In addition, we investigated the enantioselective catalysis of the reaction using alpha,alpha,alpha',alpha'-tetraaryl-1,3-dioxolan-4,5-dimethanol alcohol (TADDOL). We found that TADDOL lowered the energy
Study of microbial adhesion on some wood species: theoretical prediction.
Soumya, El abed; Mohamed, Mostakim; Fatimazahra, Berguadi; Hassan, Latrache; Abdellah, Houari; Fatima, Hamadi; Saad, Ibnsouda koraichi
2011-01-01
The initial interaction between microorganisms and substrata is mediated by physicochemical forces, which in turn originate from the physicochemical surface properties of both interacting phases. In this context, we have determined the physicochemical proprieties of all microorganisms isolated from cedar wood decay in an old monument at the Medina of Fez-Morocco. The cedar wood was also assayed in terms of hydrophobicity and electron dono-r-electron acceptor (acid-base) properties. Investigations of these two aspects were performed by contact angles measurements via sessile drop technique. Except Bacillus subtilis strain (deltaGiwi 0) and can therefore be considered as hydrophilic while cedar wood revealed a hydrophobic character (deltaGiwi = -58.81 mi m(-2)). All microbial strains were predominantly electron donor. The results show also that all strains were weak electron acceptors. Cedar wood exhibits a weak electron donor/acceptor character. Based on the thermodynamic approach, the Lifshitz-van der Waals interaction free energy, the acid-basic interactions free energy, the total interaction free energy between the microbial cells and six different wood species (cedar, oak, beech, ash, pine and teak) in aqueous media was calculated and used to predict which microbial strains have a higher ability to adhere to wooden surfaces. Except of weak wood, for all the situations studied, generalizations concerning the adhesion of the microbiata on wood species cannot be made and the microbial adhesion on wooden substrata was dependent on wood species and microorganismstested.
A theoretical study on vomitoxin and its tautomers
Energy Technology Data Exchange (ETDEWEB)
Tuerker, Lemi [Middle East Technical University, Department of Chemistry, 06531 Ankara (Turkey)], E-mail: lturker@metu.edu.tr; Guemues, Selcuk [Middle East Technical University, Department of Chemistry, 06531 Ankara (Turkey); Yuezuencue Yil Universitesi, Kimya Boeluemue, 65080 Kampues, Van (Turkey)
2009-04-15
In the present work, the structural and electronic properties of vomitoxin (deoxynivalenol, a mycotoxin) and all of its possible tautomers have been investigated by the application of B3LYP/6-31G(d,p) type quantum chemical calculations. According to the results of the calculations, tautomer V{sub 4} has been found to be the most stable one among all the structures both in the gas and aqueous phases. The calculations also indicated that, vomitoxin and V{sub 2} possess the deepest and the highest lying HOMO levels, respectively. Hence, V{sub 2} is to be more susceptible to oxidations than the others. On the other hand, V{sub 5}(S) and vomitoxin have the lowest and the next lowest LUMO energies, respectively. Whereas, V{sub 1} and V{sub 2} possess quite highly lying (within the group) LUMO energy levels which result in comparatively unfavorable reduction potentials. Some important geometrical and physicochemical properties and the calculated IR spectra of the systems have also been reported in the study.
Theoretical kinetic study of the low temperature oxidation of ethanol
Fournet, René; Bounaceur, Roda; Molière, Michel
2009-01-01
In order to improve the understanding of the low temperature combustion of ethanol, high-level ab initio calculations were performed for elementary reactions involving hydroxyethylperoxy radicals. These radicals come from the addition of hydroxethyl radicals (?CH3CHOH and ?CH2CH2OH) on oxygen molecule. Unimolecular reactions involving hydroxyethylperoxy radicals and their radical products were studied at the CBS-QB3 level of theory. The results allowed to highlight the principal ways of decomposition of these radicals. Calculations of potential energy surfaces showed that the principal channels lead to the formation of HO2 radicals which can be considered, at low temperature, as slightly reactive. However, in the case of CH3CH(OOH)O? radicals, a route of decomposition yields H atom and formic peracid, which is a branching agent that can strongly enhance the reactivity of ethanol in low temperature oxidation. In addition to these analyses, high-pressure limit rate constants were derived in the temperature rang...
Theoretical study on the constricted flow phenomena in arteries
Sen, S.; Chakravarty, S.
2012-12-01
The present study is dealt with the constricted flow characteristics of blood in arteries by making use of an appropriate mathematical model. The constricted artery experiences the generated wall shear stress due to flow disturbances in the presence of constriction. The disturbed flow in the stenosed arterial segment causes malfunction of the cardiovascular system leading to serious health problems in the form of heart attack and stroke. The flowing blood contained in the stenosed artery is considered to be non-Newtonian while the flow is treated to be two-dimensional. The present pursuit also accounts for the motion of the arterial wall and its effect on local fluid mechanics. The flow analysis applies the time-dependent, two-dimensional incompressible nonlinear Navier-Stokes equations for non-Newtonian fluid representing blood. An extensive quantitative analysis presented at the end of the paper based on large scale numerical computations of the quantities of major physiological significance enables one to estimate the constricted flow characteristics in the arterial system under consideration which deviates significantly from that of normal physiological flow conditions.
Theoretical study of trans-cis photoisomerism in polymethine cyanines
Momicchioli, Fabio; Baraldi, Ivan; Berthier, Gaston
1988-06-01
The trans-cis photoisomerism of polymethine dyes has been interpreted so far using different and rather inconsistent models of the potential energy surfaces. In order to search for a unified electronic model, we tackled the problem again from an intramolecular point of view. Our study consisted in qualitative MO considerations followed by explicit (CS INDO) calculations of the S 0, T 1 and S 1 potential energy curves for a proper model system: pentamethine cyanine isomerizing around the 2-3 and 3-4 bonds. Torsional energy levels for the calculated potential curves were also obtained. The main conclusions are: (i) the photoreaction proceeds through a "non-spectroscopic" (perp) S 1 minimum which exists also in the isolated molecule, (ii) this twisted excited species has charge transfer character (TICT), as opposed to the biradicaloid character of the "non-spectroscopic" S 1 minimum involved in the trans→cis photoisomerization of olefines (e.g., stilbene). The possible consequences on the dynamics of the excited state relaxation in non-polar solvents are envisaged.
Theoretical design study of the MSFC wind-wheel turbine
Frost, W.; Kessel, P. A.
1982-01-01
A wind wheel turbine (WWT) is studied. Evaluation of the probable performance, possible practical applications, and economic viability as compared to other conventional wind energy systems is discussed. The WWT apparatus is essentially a bladed wheel which is directly exposed to the wind on the upper half and exposed to wind through multiple ducting on the lower half. The multiple ducts consist of a forward duct (front concentrator) and two side ducts (side concentrators). The forced rotation of the wheel is then converted to power through appropriate subsystems. Test results on two simple models, a paper model and a stainless steel model, are reported. Measured values of power coefficients over wind speeds ranging from 4 to 16 m/s are given. An analytical model of a four bladed wheel is also developed. Overall design features of the wind turbine are evaluated and discussed. Turbine sizing is specified for a 5 and 25 kW machine. Suggested improvements to the original design to increase performance and performance predictions for an improved WWT design are given.
Theoretical and experimental studies of a magnetically actuated valveless micropump
Ashouri, Majid; Behshad Shafii, Mohammad; Moosavi, Ali
2017-01-01
This paper presents the prototype design, fabrication, and characterization of a magnetically actuated micropump. The pump body consists of three nozzle/diffuser elements and two pumping chambers connected to the ends of a flat-wall pumping cylinder. A cylindrical permanent magnet placed inside the pumping cylinder acts as a piston which reciprocates by using an external magnetic actuator driven by a motor. The magnetic piston is covered by a ferrofluid to provide self-sealing capability. A prototype composed of three bonded layers of polymethyl-methacrylate (PMMA) has been fabricated. Water has been successfully pumped at pressures of up to 750 Pa and flow rates of up to 700 µl min-1 while working at the piston actuation frequency of 4 and 5 Hz, respectively. 3D numerical simulations are also carried out to study the performance of the pump. The best experimental and numerical volumetric efficiency of the pump are about 7 and 8%, respectively, at the piston speed of 0.03 m s-1. The contactless external actuation feature of the design enables integration of the pump with other PMMA-based microfluidic systems with low cost and disposability.
Theoretical Studies of the Optoelectronic Properties of Semiconductor Quantum Wells.
Chao, Calvin Yi-Ping
The valence-band structure of a semiconductor quantum well is calculated based on the multiband effective -mass theory. A unitary transformation is found to diagonalize the six-by-six Luttinger-Kohn Hamiltonian into two three -by-three blocks, making the computation more efficient. With this new formulation, the effect of strain on the band structure is studied systematically for both the compressional and tensile strain. The importance of the coupling between the heavy-hole, light-hole bands and the spin-orbit split -off bands is especially pointed out. The resonant tunneling of holes through a double -barrier structure is investigated using a transfer-matrix technique. It is shown that the strong mixing between the heavy holes and the light holes results in a totally different I-V characteristic from that predicted previously by the parabolic-band model. The exciton equation in momentum space is solved by using a modified Gaussian quadrature method. The exact solutions for a pure-two-dimensional exciton are derived by means of the Mehler-Fock transform, and the accuracy of the quadrature method is checked by comparing the numerical solutions against the exact solutions. A complete theory for quantum-well excitons is developed taking into account the effects of the valence -band mixing and the intersubband Coulomb interaction. Optical absorption spectra are calculated and compared to experimental data. The comparison demonstrates that the theory explains very well the quantum-confined Stark effect, the polarization selection rule, the coupling between the interwell and intrawell excitons in a multiwell structure, and the anticrossing between the ground state of a light-hole exciton and the excited state of a heavy-hole exciton observed experimentally.
Theoretical studies in nuclear reactions and nuclear structure. Progress report
Energy Technology Data Exchange (ETDEWEB)
1992-05-01
Research in the Maryland Nuclear Theory Group focusses on problems in four basic areas of current relevance. Hadrons in nuclear matter; the structure of hadrons; relativistic nuclear physics and heavy ion dynamics and related processes. The section on hadrons in nuclear matter groups together research items which are aimed at exploring ways in which the properties of nucleons and the mesons which play a role in the nuclear force are modified in the nuclear medium. A very interesting result has been the finding that QCD sum rules supply a new insight into the decrease of the nucleon`s mass in the nuclear medium. The quark condensate, which characterizes spontaneous chiral symmetry breaking of the late QCD vacuum, decreases in nuclear matter and this is responsible for the decrease of the nucleon`s mass. The section on the structure of hadrons contains progress reports on our research aimed at understanding the structure of the nucleon. Widely different approaches are being studied, e.g., lattice gauge calculations, QCD sum rules, quark-meson models with confinement and other hedgehog models. A major goal of this type of research is to develop appropriate links between nuclear physics and QCD. The section on relativistic nuclear physics represents our continuing interest in developing an appropriate relativistic framework for nuclear dynamics. A Lorentz-invariant description of the nuclear force suggests a similar decrease of the nucleon`s mass in the nuclear medium as has been found from QCD sum rules. Work in progress extends previous successes in elastic scattering to inelastic scattering of protons by nuclei. The section on heavy ion dynamics and related processes reports on research into the e{sup +}e{sup {minus}} problem and heavy ion dynamics.
Theoretical studies in nuclear reactions and nuclear structure
Energy Technology Data Exchange (ETDEWEB)
1992-05-01
Research in the Maryland Nuclear Theory Group focusses on problems in four basic areas of current relevance. Hadrons in nuclear matter; the structure of hadrons; relativistic nuclear physics and heavy ion dynamics and related processes. The section on hadrons in nuclear matter groups together research items which are aimed at exploring ways in which the properties of nucleons and the mesons which play a role in the nuclear force are modified in the nuclear medium. A very interesting result has been the finding that QCD sum rules supply a new insight into the decrease of the nucleon's mass in the nuclear medium. The quark condensate, which characterizes spontaneous chiral symmetry breaking of the late QCD vacuum, decreases in nuclear matter and this is responsible for the decrease of the nucleon's mass. The section on the structure of hadrons contains progress reports on our research aimed at understanding the structure of the nucleon. Widely different approaches are being studied, e.g., lattice gauge calculations, QCD sum rules, quark-meson models with confinement and other hedgehog models. A major goal of this type of research is to develop appropriate links between nuclear physics and QCD. The section on relativistic nuclear physics represents our continuing interest in developing an appropriate relativistic framework for nuclear dynamics. A Lorentz-invariant description of the nuclear force suggests a similar decrease of the nucleon's mass in the nuclear medium as has been found from QCD sum rules. Work in progress extends previous successes in elastic scattering to inelastic scattering of protons by nuclei. The section on heavy ion dynamics and related processes reports on research into the e{sup +}e{sup {minus}} problem and heavy ion dynamics.
Theoretical and experimental studies on emissions from wood combustion
Energy Technology Data Exchange (ETDEWEB)
Skreiberg, Oeyvind
1997-12-31
This thesis discusses experiments on emissions from wood log combustion and single wood particle combustion, both caused by incomplete combustion and emissions of nitric and nitrous oxide, together with empirical and kinetic NO{sub x} modelling. Experiments were performed in three different wood stoves: a traditional stove, a staged air stove and a stove equipped with a catalytic afterburner. Ideally, biomass fuel does not give a net contribution to the greenhouse effect. However, incomplete combustion was found to result in significant greenhouse gas emissions. Empirical modelling showed the excess air ratio and the combustion chamber temperature to be the most important input variables controlling the total fuel-N to NO{sub x} conversion factor. As the result of an international round robin test of a wood stove equipped with a catalytic afterburner, particle emission measurements were found to be the best method to evaluate the environmental acceptability of the tested stove, since the particle emission level was least dependent of the national standards, test procedures and calculation procedures used. In batch single wood particle combustion experiments on an electrically heated small-scale fixed bed reactor the fuel-N to NO conversion factor varied between 0.11-0.86 depending on wood species and operating conditions. A parameter study and homogeneous kinetic modelling on a plug flow reactor showed that, depending on the combustion compliance in question, there is an optimum combination of primary excess air ratio, temperature and residence time that gives a maximum conversion of fuel-N to N{sub 2}. 70 refs., 100 figs., 26 tabs.
Theoretical Study of Amplitude Modulation Application during Radio Frequency Electrocoagulation
Directory of Open Access Journals (Sweden)
V. A. Karpuhin
2015-01-01
Full Text Available This article concerns the investigation results of influence of the amplitude-modulated acting signal parameters on the thermoelectric characteristics of biological tissues for a specified geometry of the working electrode section during RF mono-polar electrocoagulation. The geometric model ‘electrode - a biological tissue’ was suggested to study the distribution of power and temperature fields in biological tissue during mono-polar coagulation. The model of biological tissue is represented as a cylinder and the needle electrode is an ellipsoid immersed in the biological tissue. The heat and quasi-electrostatics equations are used as a mathematical model. These equations are solved in Comsol Multiphysics environment.As a result, we have got the following findings: the technique of calculating parameters of the PAM acting signal which has a fixed carrier frequency for the needle electrode of a specified geometry and the immersion depth in biological tissues is suggested. Parameters of PAM signal are determined for this electrode geometry. These parameters provide a 60 ... 80°C heating range of biological tissues near the working part of the tool for different amplitudes of acting signal during RF coagulation. It has been found out that both the temperature and the relaxation frequency of biological tissue depend on exposure time for the needle electrode of a specified geometry and immersion depth of the working part of tool into biological tissue.It is shown that the relaxation frequency of the biological tissue, subjected to the radiofrequency pulses, linearly depends on its heating temperature and can be used as a numerical criterion for maintaining the specified temperature conditions. It is found that the relaxation frequency of the biological tissue depends on the contact area of the tool working part and biological tissues. To reduce this dependence it is necessary to provide automatic current control of the output action.
Directory of Open Access Journals (Sweden)
Karapeychik Igor M.
2013-03-01
Full Text Available Within the frameworks of the author’s concept of the potential of an enterprise as the ability to conduct its immanently appropriate activity and also the idea of presentation of the size of the potential in the form of potential function from parameters of the state of an enterprise and foreign economic environment the article develops a scientific and methodical approach to construction and analysis of the potential function of an enterprise. The offered approach envisages building an economic and mathematical model of an enterprise of the optimisation type with consideration of environmental factors, determination of the size of economic potential as a maximum possible (optimal with the set condition of an enterprise and external environment of net income, statistical test of the model with possible values of external parameters (formation of statistical sampling of the graph of the potential function of an enterprise and application of statistical methods including methods of correlation, factor and regression analysis, for the study of its properties. Operability of this approach is shown on the example of the study of properties of the potential function of a model enterprise. In the course of approbation the article demonstrates its ability to reveal specific features of impact of external factors on economic potential of an enterprise; establishes, as a common regularity, differential influence of various environmental factors, caused not only by the nature of these factors, but also production and economic specific features and specific state of an enterprise. The article shows that the quantitative values of the force of influence of the said factors upon the value of economic potential, obtained during statistical analysis of the potential function of an enterprise, could serve as an instrument of ranking these factors by the priority level in the goal setting tasks at the stage of formation of the strategy of enterprise development
Theoretical and computational studies of small jammed systems
Gao, Guo-Jie Jason
We focus on static and slowly driven granular materials modeled as frictionless, spherical grains that interact via soft, purely repulsive contact forces. This thesis will be organized into three related projects. First, we employ simulations to generate MS disk packings using an algorithm where we successively grow or shrink the particles isotropically and minimize the total energy at each step until particles are just at contact. We focus on small systems and are able to enumerate nearly all of the possible MS packings. We found several remarkable features of the frequency distribution. For example, the frequency grows exponentially with increasing packing fraction. In addition, distinct mechanically stable packings within do occur with frequencies that differ by orders of magnitude, which contradicts the equal-probability assumption of Edwards' and other statistical mechanical descriptions. In the second project, we enumerate and classify nearly all of the possible mechanically stable (MS) packings of bidipserse mixtures of frictionless disks in small sheared systems. We find that MS packings form continuous geometrical families, where each family is defined by its particular network of particle contacts. We also monitor the dynamics of MS packings along geometrical families by applying quasistatic simple shear strain at zero pressure. For small numbers of particles, we find that the dynamics is deterministic and highly contracting. In studies with N > 16, we observe an increase in the period and random splittings of the trajectories caused by bifurcations in configuration space. We argue that the ratio of the splitting and contraction rates in large systems will determine the distribution of MS-packing geometrical families visited in steady-state. Finally, we perform simulations of sedimenting frictionless disks to generate mechanically stable (MS) packings in small 2D systems and compare these results to similarly designed experiments. In both experiments and
Theoretical study of ultraviolet induced photodissociation dynamics of sulfuric acid
Energy Technology Data Exchange (ETDEWEB)
Murakami, Tatsuhiro; Ohta, Ayumi; Suzuki, Tomoya; Ikeda, Kumiko [Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-Cho, Chiyoda-ku, Tokyo 102-8554 (Japan); Danielache, Sebastian O. [Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-Cho, Chiyoda-ku, Tokyo 102-8554 (Japan); Earth-Life Science Institute (ELSI), Tokyo Institute of Technology (Japan); Department of Environmental Science and Techonology, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Yoohama 226-8502 (Japan); Nanbu, Shinkoh, E-mail: shinkoh.nanbu@sophia.ac.jp [Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-Cho, Chiyoda-ku, Tokyo 102-8554 (Japan)
2015-05-01
Highlights: • Photodissociation dynamics of H{sub 2}SO{sub 4} at low-lying electronically excited states were investigated. • Photochemical processes were simulated by on-the-fly ab initio MD. • Sulfuric acid after the excitation to the S{sub 1} state dissociated to HSO{sub 4}(1{sup 2}A″) + H({sup 2}S). • Sulfuric acid after the excitation to the S{sub 2} state dissociated to HSO{sub 4}(2{sup 2}A″) + H({sup 2}S). • The energy region of the UV spectra where NMD fractionation may occur is predicted. - Abstract: Photodissociation dynamics of sulfuric acid after excitation to the first and second excited states (S{sub 1} and S{sub 2}) were studied by an on-the-fly ab initio molecular dynamics simulations based on the Zhu–Nakamura version of the trajectory surface hopping (ZN-TSH). Forces acting on the nuclear motion were computed on-the-fly by CASSCF method with Dunning’s augmented cc-pVDZ basis set. It was newly found that the parent molecule dissociated into two reaction-channels (i) HSO{sub 4}(1{sup 2}A″) + H({sup 2}S) by S{sub 1}-excitation, and (ii) HSO{sub 4}(2{sup 2}A″) + H({sup 2}S) by S{sub 2}-excitation. The direct dissociation dynamics yield products different from the SO{sub 2} + 2OH fragments often presented in the literature. Both channels result in the same product and differs only in the electronic state of the HSO{sub 4} fragment{sub .} The trajectories running on S{sub 2} do not hop with S{sub 0} and a nonadiabatic transition happens at the S{sub 2}–S{sub 1} conical intersection located at a longer OH bond-length than the S{sub 1}–S{sub 0} intersection producing an electronic excited state (2{sup 2}A″) of HSO{sub 4} product.
Centrifugation. A theoretical study of oxygen enrichment by centrifugation
Energy Technology Data Exchange (ETDEWEB)
Kierkegaard, P.; Raetz, E.
1998-12-01
In the present paper we first investigate what happens if we fill a cylinder with air, close it and rotate it. The results show that no matter which peripheral speed is used, it is not possible by means of the radial separation effect alone, to enrich the oxygen concentration from the previous 21% to more then 23.3%, which is of no practical value. In case of a too low enrichment in one centrifuge, the wanted material from this centrifuge can be used as an input for a second centrifuge and so on, in this way forming a cascade of centrifuges. Oxygen will be enriched in each step, until the desired concentration is reached. Cascading was the technology in the very beginning by enrichment plants for uraniumhexaflouride, used for atomic weapons and nuclear power plants. In this study we try to avoid cascading by aiming for higher separation factors. Therefore, we next investigate the possibilities of using a countercurrent centrifuge where in principle the enriched gas is subjected to several centrifugation in the same centrifuge. The calculations show, that in this way it is possible to produce nearly a 100% pure oxygen (polluted with some heavier molecules like argon) in one machine. Our third step was to calculate the amount of oxygen produced per hour. Using a countercurrent centrifuge of the Zippe type, 100 cm high and 20 cm in diameter, it is or will be possible in the near future to produce 17 g enriched air per hour enriched to 50% oxygen. That corresponds to processing 1 m{sup 3} atmospherical air in the period of approximately 24 hours. This is not very impressive. Our fourth step was to estimate the amount of power used for producing this amount of oxygen. A rough, but complicated, estimate shows that the power consumption at the production level will be about the double of the consumption used today. The overall conclusion is, that centrifugation as a production method for oxygen (or nitrogen) will not be competitive with the currently used method in the
Energy Technology Data Exchange (ETDEWEB)
Oprisan, Sorinel Adrian [Department of Psychology, University of New Orleans, New Orleans, LA (United States)]. E-mail: soprisan@uno.edu
2001-11-30
There has been increased theoretical and experimental research interest in autonomous mobile robots exhibiting cooperative behaviour. This paper provides consistent quantitative measures of organizational degree of a two-dimensional environment. We proved, by the way of numerical simulations, that the theoretically derived values of the feature are reliable measures of aggregation degree. The slope of the feature's dependence on memory radius leads to an optimization criterion for stochastic functional self-organization. We also described the intellectual heritages that have guided our research, as well as possible future developments. (author)
del Rio, B. G.; González, L. E.
2017-06-01
We perform ab initio molecular dynamics simulations of liquid Zn near the melting point in order to study the longitudinal and transverse dynamic properties of the system. We find two propagating excitations in both of them in a wide range of wave vectors. This is in agreement with some experimental observations of the dynamic structure factor in the region around half the position of the main peak. Moreover, the two-mode structure in the transverse and longitudinal current correlation functions had also been previously observed in high pressure liquid metallic systems. We perform a theoretical analysis in order to investigate the possible origin of such two components by resorting to mode-coupling theories. They are found to describe qualitatively the appearance of two modes in the dynamics, but their relative intensities are not quantitatively reproduced. We suggest some possible improvements of the theory through the analysis of the structure of the memory functions. We also analyze the single-particle dynamics embedded in the velocity autocorrelation function, and explain its characteristics through mode-coupling concepts.
Theoretical study on oligothiophene N-succinimidyl esters: size and push-pull effects.
Piacenza, M; Zambianchi, M; Barbarella, G; Gigli, G; Della Sala, F
2008-09-21
We report a theoretical study on the optical properties of bithiophene and terthiophene N-succinimidyl esters, which have been functionalized with a methylsulfanyl group in the alpha or the beta positions. Time-dependent density functional theory (TD-DFT) and approximate coupled-cluster singles and doubles with the resolution of identity technique (RI-CC2) calculations have been performed in the ground and excited states. The RI-CC2 results for absorption and fluorescence energies are in better qualitative agreement with experiments, whereas TD-DFT does not correctly describe the higher energy part of the absorption spectra of beta-substituted bithiophenes, due to the presence of charge-transfer states. Systems functionalized at the alpha position show a large red-shift of the main absorption and fluorescence band and a larger Stokes-shift compared to the unsubstituted species. These effects are in most cases less pronounced for the beta-substituted structures. In particular, we found that the Stokes-shift of the alpha-substituted structures is larger than the one of the beta-substituted species due to a more planar orientation of the methylsulfanyl group with respect to the neighbouring thiophene in the excited state.
Theoretical Studies of Gas Phase Elementary and Carbon Nanostructure Growth Reactions
2013-09-19
DOI: 10.1021/ct1000268. 26. A. J. Midey, T. M. Miller, A. A. Viggiano, N. C. Bera, S. Maeda, and K. Morokuma, Chemistry of VX Surrogates and Ion...THEORETICAL STUDIES OF GAS PHASE ELEMENTARY AND CARBON NANOSTRUCTURE GROWTH REACTIONS KEIJI MOROKUMA EMORY UNIVERSITY 09/19/2013 Final Report...Z39.18 30-09-2013 Final Performance Report 1 July 2010 - 30 June 2013 Theoretical Studies of Gas Phase Elementary and Carbon Nanostructure Growth
Woywod, Clemens; Csehi, András; Halász, Gábor J.; Ruud, Kenneth; Vibók, Ágnes
2014-03-01
The ground and five lowest-lying electronically excited singlet states of 2-(4-nitropyrimidin-2-yl)ethenol (NPE) have been studied theoretically using the complete active space self-consistent-field (CASSCF), Møller-Plesset second-order perturbation theory (MP2) and second-order multi-configurational perturbation theory (CASPT2) methods. The molecule can be regarded as being composed of a frame and a crane component and is characterised by the existence of two planar minima of similar energy on the ground-state potential energy (PE) surface. This work explores the possibility of an excited-state intramolecular hydrogen transfer (ESIHT) process in NPE. A hypothetical reaction coordinate has been constructed for NPE. State-averaged CASSCF and CASPT2 calculations of the six lowest-lying singlet states have been performed for the isomerisation. Adiabatic and simplified quasi-diabatic PE and transition dipole moment functions have been constructed. The computations indicate that there exist substantial barriers for the rotation process on the adiabatic PE surfaces of all the five excited states investigated. The six quasi-diabatic electronic states considered here decompose into two classes based on whether the electronic wave functions depend weakly or strongly on the nuclear displacement, subject to the effect of the torsion on relevant molecular orbitals.
Theoretical study of relative width of photonic band gap for the 3-D dielectric structure
Indian Academy of Sciences (India)
G K Johri; Akhilesh Tiwari; Saumya Saxena; Rajesh Sharma; Kuldeep Srivastava; Manoj Johri
2002-03-01
Calculations for the relative width (/0) as a function of refractive index and relative radius of the photonic band gap for the fcc closed packed 3-D dielectric microstructure are reported and comparison of experimental observations and theoretical predictions are given. This work is useful for the understanding of photonic crystals and occurrence of the photonic band gap.
Theoretical studies of the paramagnetic perovskites MTaO{sub 3} (M = Ca, Sr and Ba)
Energy Technology Data Exchange (ETDEWEB)
Ali, Zahid, E-mail: zahidf82@gmail.com [Center for Computational Materials Science, University of Malakand, Chakdara, Dir (Lower) (Pakistan); Khan, Imad; Ahmad, Iftikhar; Khan, M. Salman [Center for Computational Materials Science, University of Malakand, Chakdara, Dir (Lower) (Pakistan); Asadabadi, S. Jalali [Department of Physics, Faculty of Science, University of Isfahan, Hezar Gerib Avenue, Isfahan, 81744 (Iran, Islamic Republic of)
2015-07-15
In the present density functional studies, structural, mechanical and magneto-electronic properties of CaTaO{sub 3,} SrTaO{sub 3} and BaTaO{sub 3} perovskites have been investigated. The calculated structural parameters by DFT and analytical methods are found consistent with the experiments. The analytically calculated tolerance factors of these compounds as well as their mechanical properties show that they are stable in the cubic phase. Furthermore elastic properties show that these materials are ductile in nature and confirm that BaTaO{sub 3} is harder than the rest compounds. The calculated spin dependent magneto-electronic properties reveal the paramagnetic metallic nature of these compounds. The electrical conductivity curve demonstrates significant conductivity above room temperature. On the basis of the presented properties it is expected that these compounds could be efficient electrode materials and need experimental investigations. - Highlights: • MTaO{sub 3} (M = Ca, Sr and Ba) perovskites are investigated theoretically in the frame work of density functional theory. • Mechanical properties explain the stability of these compounds and show that BaTaO{sub 3} is more ductile. • The magneto-electronic studies reveal the paramagnetic metallic nature of these compounds. • Significant electrical conductivity is observed above room temperature.
Theoretical study of the adsorption of histidine amino acid on graphene
Rodríguez, S. J.; Makinistian, L.; Albanesi, E.
2016-04-01
Previous studies have demonstrated how the interactions between biomolecules and graphene play a crucial role in the characterization and functionalization of biosensors. In this paper we present a theoretical study of the adsorption of histidine on graphene using density functional theory (DFT). In order to evaluate the relevance of including the carboxyl (-COOH) and amino (-NH2) groups in the calculations, we considered i) the histidine complete (i.e., with its carboxyl and its amino groups included), and ii) the histidine’s imidazole ring alone. We calculated the density of states for the two systems before and after adsorption. Furthermore, we compared the results of three approximations of the exchange and correlation interactions: local density (LDA), the generalized gradients by Perdew, Burke and Ernzerhof (GGA-PBE), and one including van der Waals forces (DFT-D2). We found that the adsorption energy calculated by DFT-D2 is higher than the other two: Eads-DFT-D2 >E ads-LDA >E ads-GGA . We report the existence of charge transfer from graphene to the molecule when the adsorption occurs; this charge transfer turns up to be greater for the complete histidine than for the imidazole ring alone. Our results revealed that including the carboxyl and amino groups generates a shift in the states of imidazole ring towards EF .
Armaković, Stevan; Armaković, Sanja J; Abramović, Biljana F
2016-10-01
Antihistamines are frequently used pharmaceuticals that treat the symptoms of allergic reactions. Loratadine (LOR) is an active component of the second generation of selective antihistaminic pharmaceutical usually known as Claritin. Frequent usage of this type of pharmaceuticals imposes the need for understanding their fundamental reactive properties. In this study we have theoretically investigated reactive properties of LOR using both density functional theory (DFT) calculations and molecular dynamics (MD) simulations. DFT study is used for collecting information related to the molecule stability, structure, frontier molecular orbitals, quantum molecular descriptors, charge distribution, molecular electrostatic potential surfaces, charge polarization, and local reactivity properties according to average local ionization energy surfaces. Based on these results, N24 atom of pyridine ring and oxygen atom O1 were identified with nucleophilic nature. In order to collect the information necessary for the proposition of degradation compounds we also calculated bond dissociation energies (BDE) for hydrogen abstraction and single acyclic bonds as well. According to BDE, the oxidation is likely to occur in the piperidine and cycloheptane rings. MD simulations were used in order to understand the interactions with water through radial distribution functions (RDF). Based on RDFs the most important interactions with solvent are determined for carbon atom C5, chlorine atom Cl15, and oxygen atom O1. Collected results based on DFT calculations and MD simulations provided information important for suggestion of possible degradation compounds. Covalent and noncovalent interactions between LOR and (•)OH have also been investigated.
Spectral investigation and theoretical study of zwitterionic and neutral forms of quinolinic acid
Karabacak, M.; Sinha, L.; Prasad, O.; Bilgili, S.; Sachan, Alok K.; Asiri, A. M.; Atac, A.
2015-09-01
In this study, molecular structure and vibrational analysis of quinolinic acid (2,3-pyridinedicarboxylic acid), in zwitterionic and neutral forms, were presented using FT-IR, FT-Raman, NMR, UV experimental techniques and quantum chemical calculations. FT-IR and FT-Raman spectra of 2,3-pyridinedicarboxylic acid (2,3-PDCA) in the solid phase were recorded in the region 4000-400 cm-1 and 3500-0 cm-1, respectively. The geometrical parameters and energies were obtained for zwitter and neutral forms by using density functional theory (DFT) at B3LYP/6-311++G(d,p) level of theory. 3D potential energy scan was performed by varying the selected dihedral angles using M06-2X and B3LYP functionals at 6-31G(d) level of theory and thus the most stable conformer of the title compound was determined. The most stable conformer was further optimized at higher level and vibrational wavenumbers were calculated. Theoretical vibrational assignment of 2,3-PDCA, using percentage potential energy distribution (PED) was done with MOLVIB program. 13C and 1H NMR spectra were recorded in DMSO. Chemical shifts were calculated at the same level of theory. The UV absorption spectra of the studied compound in ethanol and water were recorded in the range of 200-400 nm. The optimized geometric parameters were compared with experimental data.
An in-depth analysis of theoretical frameworks for the study of care coordination
Directory of Open Access Journals (Sweden)
Sabine Van Houdt
2013-06-01
Full Text Available Introduction: Complex chronic conditions often require long-term care from various healthcare professionals. Thus, maintaining quality care requires care coordination. Concepts for the study of care coordination require clarification to develop, study and evaluate coordination strategies. In 2007, the Agency for Healthcare Research and Quality defined care coordination and proposed five theoretical frameworks for exploring care coordination. This study aimed to update current theoretical frameworks and clarify key concepts related to care coordination. Methods: We performed a literature review to update existing theoretical frameworks. An in-depth analysis of these theoretical frameworks was conducted to formulate key concepts related to care coordination.Results: Our literature review found seven previously unidentified theoretical frameworks for studying care coordination. The in-depth analysis identified fourteen key concepts that the theoretical frameworks addressed. These were ‘external factors’, ‘structure’, ‘tasks characteristics’, ‘cultural factors’, ‘knowledge and technology’, ‘need for coordination’, ‘administrative operational processes’, ‘exchange of information’, ‘goals’, ‘roles’, ‘quality of relationship’, ‘patient outcome’, ‘team outcome’, and ‘(interorganizational outcome’.Conclusion: These 14 interrelated key concepts provide a base to develop or choose a framework for studying care coordination. The relational coordination theory and the multi-level framework are interesting as these are the most comprehensive.
An in-depth analysis of theoretical frameworks for the study of care coordination
Directory of Open Access Journals (Sweden)
Sabine Van Houdt
2013-06-01
Full Text Available Introduction: Complex chronic conditions often require long-term care from various healthcare professionals. Thus, maintaining quality care requires care coordination. Concepts for the study of care coordination require clarification to develop, study and evaluate coordination strategies. In 2007, the Agency for Healthcare Research and Quality defined care coordination and proposed five theoretical frameworks for exploring care coordination. This study aimed to update current theoretical frameworks and clarify key concepts related to care coordination. Methods: We performed a literature review to update existing theoretical frameworks. An in-depth analysis of these theoretical frameworks was conducted to formulate key concepts related to care coordination. Results: Our literature review found seven previously unidentified theoretical frameworks for studying care coordination. The in-depth analysis identified fourteen key concepts that the theoretical frameworks addressed. These were ‘external factors’, ‘structure’, ‘tasks characteristics’, ‘cultural factors’, ‘knowledge and technology’, ‘need for coordination’, ‘administrative operational processes’, ‘exchange of information’, ‘goals’, ‘roles’, ‘quality of relationship’, ‘patient outcome’, ‘team outcome’, and ‘(interorganizational outcome’. Conclusion: These 14 interrelated key concepts provide a base to develop or choose a framework for studying care coordination. The relational coordination theory and the multi-level framework are interesting as these are the most comprehensive.
Energy Technology Data Exchange (ETDEWEB)
Fernandez, A.M.; Timon, V.; Cubero, J. J.; Sanchez-Ledesma, D. M.; Gutierrez-Nebot, L.; Martinez, J. J.; Romero, C.; Labajo, M.; Melon, A.; Barrios, I.
2013-10-01
New data about the physico-chemical, microstructural and crystal-chemical properties of the mineral paligorskite from Torrejon el Rubio (Caceres, Spain) were obtained by a combination of experimental techniques (XRD, FRX, FTIR, TG-DSC, SEM and chemical analyses), as well as geometry optimization by means of the Density Functional Theory (DFT). This study demonstrates the applicability of the mixed theoretical-experimental work to characterize and understand the properties of clay minerals used in technological applications and environmental remediation. (Author)
Dolan, Paul; Tsuchiya, Aki
2009-01-01
The literature on income distribution has attempted to evaluate different degrees of inequality using a social welfare function (SWF) approach. However, it has largely ignored the source of such inequalities, and has thus failed to consider different degrees of inequity. The literature on egalitarianism has addressed issues of equity, largely in relation to individual responsibility. This paper builds upon these two literatures, and introduces individual responsibility into the SWF. Results from a small-scale study of people's preferences in relation to the distribution of health benefits are presented to illustrate how the parameter values of a SWF might be determined.
Theoretical study of the C-H bond dissociation energy of acetylene
Taylor, Peter R.; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.
1990-01-01
The authors present a theoretical study of the convergence of the C-H bond dissociation energy (D sub o) of acetylene with respect to both the one- and n-particle spaces. Their best estimate for D sub o of 130.1 plus or minus 1.0 kcal/mole is slightly below previous theoretical estimates, but substantially above the value determined using Stark anticrossing spectroscopy that is asserted to be an upper bound.
Theoretical study of the oxidation mechanisms of thiophene initiated by hydroxyl radicals.
Shiroudi, Abolfazl; Deleuze, Michael S
2015-11-01
The mechanisms for the oxidation of thiophene by OH radicals under inert conditions (Ar) have been studied using density functional theory in conjunction with various exchange-correlation functionals. These results were compared with benchmark CBS-QB3 theoretical results. Kinetic rate constants were estimated by means of variational transition state theory (VTST) and the statistical Rice-Ramsperger-Kassel-Marcus (RRKM) theory. Effective rate constants were calculated via a steady-state analysis based upon a two-step model reaction mechanism. In line with experimental results, the computed branching ratios indicate that the most kinetically efficient process involves OH addition to a carbon atom adjacent to the sulfur atom. Due to the presence of negative activation energies, pressures larger than 10(4) bar are required to reach the high-pressure limit. Nucleus-independent chemical shift indices and natural bond orbital analysis show that the computed activation energies are dictated by changes in aromaticity and charge-transfer effects due to the delocalization of lone pairs from sulfur to empty π(*) orbitals. Graphical Abstract CBS-QB3 energy profiles for the reaction pathways 1-3 characterizing the oxidation of thiophene by hydroxyl radicals into the related products.
Amino acids as corrosion inhibitors for copper in acidic medium: Experimental and theoretical study
Directory of Open Access Journals (Sweden)
Milošev Ingrid
2013-01-01
Full Text Available Experimental electrochemical methods combined with quantum chemical calculations and molecular dynamics simulations were used to investigate the possibility of use various amino acids as “green” corrosion inhibitors for copper in 0.5 M HCl solution. Among eleven amino acids studied, cysteine achieved the highest inhibitor effectiveness reaching 52% at 10 mM concentration. Other amino acids reached achieved effectiveness less than 25%, some of them even acted as corrosion accelerators. Based on the experimental results, theoretical calculations and simulations were focused on cysteine and alanine. The electronic and reactivity parameters of their protonated forms in electrical double layer were evaluated by density functional calculations. In addition, molecular dynamic simulations were introduced to follow the adsorption behaviour of these two amino acids at the Cu(111 surface in the electrolyte solution. The results indicate that the orientation of both molecules is nearly parallel to the surface except of ammonium group which is directed away from the surface. Therefore, as the orientation of the cysteine and alanine molecules at the surface is similar, thiol functional group is responsible for superior inhibition efficiency of cysteine.
Theoretical study of NMR, infrared and Raman spectra on triple-decker phthalocyanines
Energy Technology Data Exchange (ETDEWEB)
Suzuki, Atsushi; Oku, Takeo [Department of Materials Science, The University of Shiga Prefecture 2500 Hassaka, Hikone, Shiga, 522-8533 (Japan)
2016-02-01
Electronic structures and magnetic properties of multi-decker phthalocyanines were studied by theoretical calculation. Electronic structures, excited processes at multi-states, isotropic chemical shifts of {sup 13}C, {sup 14}N and {sup 1}H-nuclear magnetic resonance (NMR), principle V-tensor in electronic field gradient (EFG) tensor and asymmetry parameters (η), vibration mode in infrared (IR) and Raman spectra of triple-decker phthalocyanines were calculated by density functional theory (DFT) and time-dependent DFT using B3LYP as basis function. Electron density distribution was delocalized on the phthalocyanine rings with electron static potential. Considerable separation of chemical shifts in {sup 13}C, {sup 14}N and {sup 1}H-NMR was originated from nuclear spin interaction between nitrogen and carbon atoms, nuclear quadrupole interaction based on EFG and η of central metal under crystal field. Calculated optical absorption at multi-excited process was derived from overlapping π-orbital on the phthalocyanine rings. The vibration modes in IR and Raman spectra were based on in-plane deformation and stretching vibrations of metal-ligand coordination bond on the deformed structure.
A DFT theoretical study of heats of formation and detonation properties of nitrogen-rich explosives.
Jaidann, Mounir; Roy, Sandra; Abou-Rachid, Hakima; Lussier, Louis-Simon
2010-04-15
We present density-functional theory predictions and analysis of some properties of synthesized high-nitrogen compounds 3,6-diazido-1,2,4,5-tetrazine (DiAT) and N-oxides of 3,3'-azo-bis(6-amino-1,2,4,5-tetrazine) (DAATO) together with 3,6-di(hydrazino)-1,2,4,5-tetrazine (DHT) and 3,3'-azo-bis(6-amino-1,2,4,5-tetrazine) (DAAT) for which experimental data are available. In this work the reference molecules DHT and DAAT have been studied in order to validate the theoretical approach and facilitate further progress developments for the molecules of interest such as DiAT and DAATO. Geometries of all compounds have been optimized employing the B3LYP density-functional method in conjunction with 6-311++G(3d,3p) basis sets. The energy content of the molecules in the gas phase is evaluated by calculating standard enthalpies of formation, using isodesmic reaction paths. We also include estimates of the condensed-phase heats of formation and heats of sublimation in the framework of the Politzer approach. The obtained results show that DiAT compound has the highest heat of formation (231 kcal/mol) in comparison with those of DHT, DAAT and DAATO molecules. The detonation velocity and pressure have also been estimated for these molecules using the Stine method.
An improved theoretical approach to the empirical corrections of density functional theory
Lii, Jenn-Huei; Hu, Ching-Han
2012-02-01
An empirical correction to density functional theory (DFT) has been developed in this study. The approach, called correlation corrected atomization-dispersion (CCAZD), involves short- and long-range terms. Short-range correction consists of bond ( 1,2-) and angle ( 1,3-) interactions, which remedies the deficiency of DFT in describing the proto-branching stabilization effects. Long-range correction includes a Buckingham potential function aiming to account for the dispersion interactions. The empirical corrections of DFT were parameterized to reproduce reported Δ H f values of the training set containing alkane, alcohol and ether molecules. The Δ H f of the training set molecules predicted by the CCAZD method combined with two different DFT methods, B3LYP and MPWB1K, with a 6-31G* basis set agreed well with the experimental data. For 106 alkane, alcohol and ether compounds, the average absolute deviations (AADs) in Δ H f were 0.45 and 0.51 kcal/mol for B3LYP- and MPWB1K-CCAZD, respectively. Calculations of isomerization energies, rotational barriers and conformational energies further validated the CCAZD approach. The isomerization energies improved significantly with the CCAZD treatment. The AADs for 22 energies of isomerization reactions were decreased from 3.55 and 2.44 to 0.55 and 0.82 kcal/mol for B3LYP and MPWB1K, respectively. This study also provided predictions of MM4, G3, CBS-QB3 and B2PLYP-D for comparison. The final test of the CCAZD approach on the calculation of the cellobiose analog potential surface also showed promising results. This study demonstrated that DFT calculations with CCAZD empirical corrections achieved very good agreement with reported values for various chemical reactions with a small basis set as 6-31G*.
Convexity of Energy-Like Functions: Theoretical Results and Applications to Power System Operations
Energy Technology Data Exchange (ETDEWEB)
Dvijotham, Krishnamurthy [California Inst. of Technology (CalTech), Pasadena, CA (United States); Low, Steven [California Inst. of Technology (CalTech), Pasadena, CA (United States); Chertkov, Michael [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
2015-01-12
Power systems are undergoing unprecedented transformations with increased adoption of renewables and distributed generation, as well as the adoption of demand response programs. All of these changes, while making the grid more responsive and potentially more efficient, pose significant challenges for power systems operators. Conventional operational paradigms are no longer sufficient as the power system may no longer have big dispatchable generators with sufficient positive and negative reserves. This increases the need for tools and algorithms that can efficiently predict safe regions of operation of the power system. In this paper, we study energy functions as a tool to design algorithms for various operational problems in power systems. These have a long history in power systems and have been primarily applied to transient stability problems. In this paper, we take a new look at power systems, focusing on an aspect that has previously received little attention: Convexity. We characterize the domain of voltage magnitudes and phases within which the energy function is convex in these variables. We show that this corresponds naturally with standard operational constraints imposed in power systems. We show that power of equations can be solved using this approach, as long as the solution lies within the convexity domain. We outline various desirable properties of solutions in the convexity domain and present simple numerical illustrations supporting our results.
Convexity of Energy-Like Functions: Theoretical Results and Applications to Power System Operations
Energy Technology Data Exchange (ETDEWEB)
Dvijotham, Krishnamurthy [California Inst. of Technology (CalTech), Pasadena, CA (United States); Chertkov, Michael [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Low, Steven [California Inst. of Technology (CalTech), Pasadena, CA (United States)
2015-01-22
Power systems are undergoing unprecedented transformations with increased adoption of renewables and distributed generation, as well as the adoption of demand response programs. All of these changes, while making the grid more responsive and potentially more efficient, pose significant challenges for power systems operators. Conventional operational paradigms are no longer sufficient as the power system may no longer have big dispatchable generators with sufficient positive and negative reserves. This increases the need for tools and algorithms that can efficiently predict safe regions of operation of the power system. In this paper, we study energy functions as a tool to design algorithms for various operational problems in power systems. These have a long history in power systems and have been primarily applied to transient stability problems. In this paper, we take a new look at power systems, focusing on an aspect that has previously received little attention: Convexity. We characterize the domain of voltage magnitudes and phases within which the energy function is convex in these variables. We show that this corresponds naturally with standard operational constraints imposed in power systems. We show that power of equations can be solved using this approach, as long as the solution lies within the convexity domain. We outline various desirable properties of solutions in the convexity domain and present simple numerical illustrations supporting our results.
Pathways in coal thermolysis: a theoretical and experimental study with model compounds
Energy Technology Data Exchange (ETDEWEB)
Ekpenyong, I.A.; Virk, P.S.
1982-01-01
Fundamental aspects of coal thermolysis were investigated, including how the chemical structures of aromatics, hydroaromatics, and alcohols affect their reactivities as hydrogen donors and acceptors in coal processing. The susceptibilities of substructural entities in coals to fragmentation via a number of thermal pericyclic and free radical mechanisms were probed, as were the factors governing relative reactivities within series of such coal model compounds. The theoretical part of the work applied perturbation molecular orbital (PMO) and frontier orbital theories, in conjunction with ..pi..- and pseudo-..pi.. MO's, to the study of model compound reactivity. This enabled prediction of reactivity patterns of H-donors, H-acceptors and coal-like structures as functions of their ..pi..- and sigma-bond configurations, including heteroatomic effects. Experimentally, the liquid phase reactions of the coal model compound PhOCH/sub 2/Ph (Benzyl phenyl ether, BPE) were detailed for the first time in each of four hydronaphthalene H-donor solvents in the temperature range 220/sup 0/ to 300/sup 0/C. The thermolysis of BPE exhibited a pronounced dependence on solvent structure, both with respect to product selectivities and reaction kinetics. BPE thermolysis pathways were delineated as involving (a) rearrangement, leading to isomerization, (b) hydrogenations, leading ultimately to PhOH and PhCH/sub 3/ products, and (c) addition reactions, engendering heavy products. Pathways (b) and (c) are competitive and, in each, self-reactions of BPE-derivatives vie against reactions between these and the donor solvent. Of the detailed free radical and pericyclic reaction mechanisms postulated, the latter rationalized many more facets of the BPE results than the former. The theoretical and experimental results were appraised against previous coal thermolysis literature.
Wang, Z P; Reinhard, P -G; Suraud, E; Bruny, G; Montano, C; Feil, S; Eden, S; Abdoul-Carime, H; Farizon, B; Farizon, M; Ouaskit, S; Maerk, T D
2009-01-01
The influences of water molecules surrounding biological molecules during irradiation with heavy particles (atoms,ions) are currently a major subject in radiation science on a molecular level. In order to elucidate the underlying complex reaction mechanisms we have initiated a joint experimental and theoretical investigation with the aim to make direct comparisons between experimental and theoretical results. As a first step, studies of collisions of a water molecule with a neutral projectile (C atom) at high velocities (> 0.1 a.u.), and with a charged projectile (proton) at low velocities (< 0.1 a.u.) have been studied within the microscopic framework. In particular, time-dependent density functional theory (TDDFT) was applied to the valence electrons and coupled non-adiabatically to Molecular dynamics (MD) for ionic cores. Complementary experimental developments have been carried out to study projectile interactions with accelerated (< 10 keV) and mass-selected cluster ions. The first size distributio...
Theoretical study of Al{sub n}V{sup +} clusters and their interaction with Ar
Energy Technology Data Exchange (ETDEWEB)
Fernández, Eva María, E-mail: emfernandez@fisfun.uned.es [Departamento de Física Fundamental, Facultad de Ciencias, UNED, 28040 Madrid (Spain); Vega, Andrés; Balbás, Luis Carlos [Departamento de Física Teórica, Universidad de Valladolid, 47011 Valladolid (Spain)
2013-12-07
Recently, it has been experimentally elucidated whether a V impurity in Al{sub n}V{sup +} clusters occupies an external or an internal site by studying their interaction with argon as a function of cluster size [S. M. Lang, P. Claes, S. Neukermans, and E. Janssens, J. Am. Soc. Mass Spectrom. 22, 1508 (2011)]. In the work presented here we studied, by means of density functional theoretic calculations, the structural and electronic properties of Al{sub n}V{sup +} clusters with n = 14–21 atoms, as well as the adsorption of a single Ar atom on them. For n < 17 the lowest energy structure of Al{sub n}V{sup +} is related to that of the pure Al {sub n+1}{sup +} cluster with the V atom substituting a surface Al atom. For n ⩾ 17 the V impurity becomes embedded in the cluster, in agreement with the experimental results, and the clusters adopt a fcc-like structure instead of the icosahedral-like skeleton of pure Al {sub n+1}{sup +}. We have studied the binding energy per atom, the second energy difference, and the V and Al atom separation energies, in comparison with those of pure Al {sub n+1}{sup +}. We also studied the adsorption of atomic Ar on endohedral and exohedral V doped clusters. The optimized Ar adsorption geometries are formed with Ar on top of a surface atom (V for n < 17, and Al for n ⩾ 17) without noticeable structural distortion of the host cluster. At the critical size (n = 17) of the exohedral-endohedral transition, the calculated Ar adsorption energy exhibits a drop and the Ar-cluster distance increases drastically, indicating that Ar becomes physisorbed rather than chemisorbed. All these results confirm the assumptions made by the experimentalists when interpreting their measurements.
Validation of a Theoretical Model of Diagnostic Classroom Assessment: A Mixed Methods Study
Koh, Nancy
2012-01-01
The purpose of the study was to validate a theoretical model of diagnostic, formative classroom assessment called, "Proximal Assessment for Learner Diagnosis" (PALD). To achieve its purpose, the study employed a two-stage, mixed-methods design. The study utilized multiple data sources from 11 elementary level mathematics teachers who…
Risk-Sensitive Multiagent Decision-Theoretic Planning Based on MDP and One-Switch Utility Functions
Directory of Open Access Journals (Sweden)
Wei Zeng
2014-01-01
Full Text Available In high stakes situations decision-makers are often risk-averse and decision-making processes often take place in group settings. This paper studies multiagent decision-theoretic planning under Markov decision processes (MDPs framework with considering the change of agent’s risk attitude as his wealth level varies. Based on one-switch utility function that describes agent’s risk attitude change with his wealth level, we give the additive and multiplicative aggregation models of group utility and adopt maximizing expected group utility as planning objective. When the wealth level approaches infinity, the characteristics of optimal policy are analyzed for the additive and multiplicative aggregation model, respectively. Then a backward-induction method is proposed to divide the wealth level interval from negative infinity to initial wealth level into subintervals and determine the optimal policy in states and subintervals. The proposed method is illustrated by numerical examples and the influences of agent’s risk aversion parameters and weights on group decision-making are also analyzed.
Choy, Jaeyoo
2016-08-01
Let K be the compact Lie group USp(N / 2) or SO(N , R) . Let MnK be the moduli space of framed K-instantons over S4 with the instanton number n. By Donaldson (1984), MnK is endowed with a natural scheme structure. It is a Zariski open subset of a GIT quotient of μ-1(0) , where μ is a holomorphic moment map such that μ-1(0) consists of the ADHM data. The purpose of the paper is to study the geometric properties of μ-1(0) and its GIT quotient, such as complete intersection, irreducibility, reducedness and normality. If K = USp(N / 2) then μ is flat and μ-1(0) is an irreducible normal variety for any n and even N. If K = SO(N , R) the similar results are proven for low n and N. As an application one can obtain a mathematical interpretation of the K-theoretic Nekrasov partition function of Nekrasov and Shadchin (2004).
Rajasekar, M.; Muthu, K.; Aditya Prasad, A.; Meenakshisundaram, S. P.
2015-04-01
Single crystals of tris(allylthiourea)mercury(II) chloride (TATMC) have been grown by slow evaporation solution growth technique. It belongs to the trigonal system with noncentrosymmetric space group R3c and the cell parameters are, a = b = 11.4443(3) Å, c = 28.1142(6) Å, V = 3188.85(14) Å3, α = β = 90°, γ = 120° and Z = 6. Powder X-ray diffraction pattern reveals the crystallinity of the as-grown specimen and it closely resembles the simulated one from the single crystal XRD data. Good reflectance in the visible region is observed and the band gap energy is estimated using diffuse reflectance data by the application of Kubelka-Munk algorithm. The functional groups are identified by Fourier transform infrared spectral analysis and compared with theoretical spectrum. The crystal is stable up to the melting point and the mechanistic behavior is ascertained by microhardness studies. The second harmonic generation efficiency of TATMC is estimated by Kurtz and Perry powder technique. The first-order molecular hyperpolarizabilities of some tris(allylthiourea) complexes have been evaluated using density functional theory (DFT) employing B3LYP functional, LanL2DZ as basis set and results rationalized. The optimized geometry closely resembles the ORTEP. The Hirshfeld surface analysis is carried out using HF method with 3-21G as basis set. Investigation of the intermolecular interactions and crystal packing via Hirshfeld surface analysis, derived by single crystal XRD data, reveals the close contacts associated with strong interactions.
Whole-proteome prediction of protein function via graph-theoretic analysis of interaction maps.
Nabieva, Elena; Jim, Kam; Agarwal, Amit; Chazelle, Bernard; Singh, Mona
2005-06-01
Determining protein function is one of the most important problems in the post-genomic era. For the typical proteome, there are no functional annotations for one-third or more of its proteins. Recent high-throughput experiments have determined proteome-scale protein physical interaction maps for several organisms. These physical interactions are complemented by an abundance of data about other types of functional relationships between proteins, including genetic interactions, knowledge about co-expression and shared evolutionary history. Taken together, these pairwise linkages can be used to build whole-proteome protein interaction maps. We develop a network-flow based algorithm, FunctionalFlow, that exploits the underlying structure of protein interaction maps in order to predict protein function. In cross-validation testing on the yeast proteome, we show that FunctionalFlow has improved performance over previous methods in predicting the function of proteins with few (or no) annotated protein neighbors. By comparing several methods that use protein interaction maps to predict protein function, we demonstrate that FunctionalFlow performs well because it takes advantage of both network topology and some measure of locality. Finally, we show that performance can be improved substantially as we consider multiple data sources and use them to create weighted interaction networks. http://compbio.cs.princeton.edu/function
Theoretical study of the dynamics of atomic hydrogen adsorbed on graphene multilayers
Moaied, Mohammed; Moreno, J. A.; Caturla, M. J.; Ynduráin, Félix; Palacios, J. J.
2015-04-01
We present a theoretical study of the dynamics of H atoms adsorbed on graphene bilayers with Bernal stacking. First, through extensive density functional theory calculations, including van der Waals interactions, we obtain the activation barriers involved in the desorption and migration processes of a single H atom. These barriers, along with attempt rates and the energetics of H pairs, are used as input parameters in kinetic Monte Carlo simulations to study the time evolution of an initial random distribution of adsorbed H atoms. The simulations reveal that, at room temperature, H atoms occupy only one sublattice before they completely desorb or form clusters. This sublattice selectivity in the distribution of H atoms may last for sufficiently long periods of time upon lowering the temperature down to 0 ∘C . The final fate of the H atoms, namely, desorption or cluster formation, depends on the actual relative values of the activation barriers which can be tuned by doping. In some cases, a sublattice selectivity can be obtained for periods of time experimentally relevant even at room temperature. This result shows the possibility for observation and applications of the ferromagnetic state associated with such distribution.
Majee, Partha Sarathi; Bhattacharyya, Somnath; Gopmandal, Partha Pratim; Ohshima, Hiroyuki
2017-09-21
A theoretical study on the gel electrophoresis of a charged particle incorporating the effects of dielectric polarization and surface hydrophobicity at the particle-liquid interface is made. A simplified model based on the weak applied field and low charge density assumption is also presented and compared with the full numerical model for a nonpolarizable particle to elucidate the nonlinear effects such as double layer polarization and relaxation as well as surface conduction. The main motivation of this study is to analyze the electrophoresis of the surface functionalized nanoparticle with tunable hydrophobicity or charged fluid drop in gel medium by considering the electrokinetic effects and hydrodynamic interactions between the particle and the gel medium. An effective medium approach, in which the transport in the electrolyte saturated hydrogel medium is governed by the Brinkman equation, is adopted in the present analysis. The governing electrokinetic equations based on the conservation principles is solved numerically. The Navier-slip boundary condition along with the continuity condition of dielectric displacement are imposed on the surface of the hydrophobic polarizable particle. The impact of the slip length on the electrophoresis is profound for a thinner Debye layer, however, surface conduction effect also becomes significant for a hydrophobic particle. Impact of hydrophobicity and relaxation effects are higher for a larger particle. Dielectric polarization creates a reduction in its electrophoretic propulsion and has negligible impact at the thinner Debye length as well as lower gel screening length. This article is protected by copyright. All rights reserved.
THEORETICAL STUDY ON CORROSION INHIBITION PROPERTIES OF 2-ISOPROPYL-5-METHYLPHENOL
Directory of Open Access Journals (Sweden)
Saprizal Hadisaputra
2016-08-01
Full Text Available Corrosion inhibitors of 2-isopropyl-5-methylphenol and its derivatives has been elucidated by means of density functional theory at B3LYP/6-31G(d level of theory. Effect of electron donating and withdrawing groups such as NH2, SH, CHCH2, CH3, OH, CHO, COOH, F and NO2 on the corrosion inhibitor of 2-isopropyl-5-methylphenol derivatives also have been studied. The quantum chemical parameters such as the frontier orbital energies (EHOMO, ionization potential (I, electron affinity (A and electronegativity (χ are closely related to the corrosion inhibition efficiency (IE % of 2-isopropyl-5-methylphenol derivatives. The presence of electron donating groups increase IE % values meanwhile electron with drawing groups reduce IE % values. The enhancement of IE % follows NO2 < CHO < COOH < SH < F < CH3 < CHCH2 < OH < NH2. Electron donating NH2 group gives 96.38 % of IE %, pure 2-isopropyl-5-methylphenol IE % = 82.70 %. In contrast, electron withdrawing NO2 group gives IE % only 68.66 %. This theoretical study would have a significantly contribution for accelerating corrosion inhibitor experimental to gain optimum results.
Platinum adsorption on ceria: A comparative theoretical study of different surfaces
Ma, Dongwei; Li, Tingxian; Wang, Qinggao; Yang, Gui; He, Chaozheng; He, Bingling; Lu, Zhansheng; Yang, Zongxian
2017-02-01
A comparative study, based on the density functional theory, on the adsorption of single Pt atoms on the CeO2(111), (110), and (100) surfaces has been performed. According to the calculated adsorption energies, it is suggested that the deposited Pt atoms on the CeO2(111) surface are easy to aggregate and form nanoparticles compared with those on the CeO2(110) and (100) surfaces. Further, the interaction strength between Pt and the three CeO2 surfaces follows the order of (100) > (110) > (111). It is also found that there is a correlation between the formal oxidation state of the adsorbed Pt and its coordination number with respect to O. The Pt atom coordinated by one O atom on the CeO2 surfaces is only slightly charged and almost neutral, and that coordinately by four O atoms exclusively has the formal oxidation state of Pt2+. The possible reasons for these findings have been discussed. And the present theoretical results have been compared with the available experimental reports. It is expected that our studies will give useful insights into the shape-dependent interaction between Pt with CeO2 nanocrystals and the shape-dependent oxidation state of the deposited Pt.
Wang, Fang; Wang, Guixiang; Du, Hongchen; Zhang, Jianying; Gong, Xuedong
2011-12-01
Density functional theory calculations were performed to find comprehensive relationships between the structures and performance of a series of highly energetic cyclic nitramines. The isodesmic reaction method was employed to estimate the heat of formation. The detonation properties were evaluated by using the Kamlet-Jacobs equations based on the theoretical densities and HOFs. Results indicate the N-NO(2) group and aza N atom are effective substituents for enhancing the detonation performance. All cyclic nitramines except C11 and C21 exhibit better detonation performance than HMX. The decomposition mechanism and thermal stability of these cyclic nitramines were analyzed via the bond dissociation energies. For most of these nitramines, the homolysis of N-NO(2) is the initial step in the thermolysis, and the species with the bridged N-N bond are more sensitive than others. Considering the detonation performance and thermal stability, twelve derivatives may be the promising candidates of high energy density materials (HEDMs). The results of this study may provide basic information for the further study of this kind of compounds and molecular design of novel HEDMs.
Ivanova, Bojidarka; Spiteller, Michael
2013-02-01
The paper presented a comprehensive theoretical and experimental study on the molecular drugs-design, synthesis, isolation, physical spectroscopic and mass spectrometric elucidation of novel functionalization derivatives of Cytisine (Cyt), using nucleosidic residues. Since these alkaloids have established biochemical profile, related the binding affinity of the nicotinic acetylcholine receptors (nAChRs), particularly α7 sub-type, the presented correlation between the molecular structure and properties allowed to evaluated the highlights of the biochemical hypothesises related the Schizophrenia. The anticancer activity of α7 subtype agonists and the crucial role of the nucleoside-based medications in the cancer therapy provided opportunity for further study on the biochemical relationship between Schizophrenia and few kinds of cancers, which has been hypothesized recently. The physical electronic absorptions (EAs), circular dichroic (CD) and Raman spectroscopic (RS) properties as well as mass spectrometric (MS) data, obtained using electrospray ionization (ESI) and atmospheric-pressure chemical ionization (APCI) methods under the positive single (MS) and tandem (MS/MS) modes of operation are discussed. Taking into account reports on a fatal intoxication of Cyt, the presented data would be of interest in the field of forensic chemistry, through development of highly selective and sensitive analytical protocols. Quantum chemical method is used to predict the physical properties of the isolated alkaloids, their affinity to the receptor loop and gas-phase stabilized species, observed mass spectrometrically.
Pandey, R. S.; Kaur, Rajbir
2015-10-01
Electromagnetic electron cyclotron (EMEC) waves with temperature anisotropy in the magnetosphere of Uranus have been studied in present work. EMEC waves are investigated using method of characteristic solution by kinetic approach, in presence of AC field. In 1986, Voyager 2 encounter with Uranus revealed that magnetosphere of Uranus exhibit non-Maxwellian high-energy tail distribution. So, the dispersion relation, real frequency and growth rate are evaluated using Lorentzian Kappa distribution function. Effect of temperature anisotropy, AC frequency and number density of particles is found. The study is also extended to oblique propagation of EMEC waves in presence and absence of AC field. Through comprehensive mathematical analysis it is found that when EMEC wave propagates parallel to intrinsic magnetic field of Uranus, its growth is more enhanced than in case of oblique propagation. Results are also discussed in context to magnetosphere of Earth and also gives theoretical explanation to existence of high energetic particles observed by Voyager 2 in the magnetosphere of Uranus. The results can present a further insight into the nature of electron-cyclotron instability condition for the whistler mode waves in the outer radiation belts of Uranus or other space plasmas.
Theoretical study of protons damage in materials used in airspace equipment
Energy Technology Data Exchange (ETDEWEB)
Stenico, Gabriela V.; Buschini, Renata L.; Inocente, Guilherme F.; Mesa, Joe [Universidade Estadual Paulista (UNESP), Botucatu, SP (Brazil). Inst. de Biociencias de Botucatu. Dept. de Fisica e Biofisica; Pazianotto, Mauricio T. [Instituto Tecnologico de Aeronautica (ITA), Sao Jose dos Campos, SP (Brazil). Inst. de Estudos Avancados
2011-07-01
Full text: There is a great ongoing effort to understanding the effect of dose levels of ionizing radiation from cosmic rays (CR) received by pilots, aircraft crew and sensitive equipment (avionics). A large part of Brazil and South America are subject to the South Atlantic Magnetic Anomaly. Differently to other places in the world, few measurements exist in this region of the radiation distribution due to cosmic ray penetration as a function of altitude, which is an important ingredient in the study of protons interactions with the materials that constitute the aircraft as well as for other spacecraft and satellites components, mainly the electronic sensitive equipment. In this sense, it is relevant to know the processes of interaction of protons with Si (semiconductor material) and Ta (metal), which are widely used with this purpose. Also with the objective to decrease the damage from the interactions of protons with these materials, it is commonly used Al slice like shield. The aim of this work is to study by Monte Carlo simulation the behavior of these materials as targets with protons of energies between 300 and 400 MeV, mainly by calculating the energy deposition, the most likely path of the protons in the target, and also the ionizing process. In this sense we used two codes: the first code was the SRIM 2008 and the MCNPX v.2.5. The theoretical results will be compared with some preliminary experimental ones obtained by IEAv (Instituto de Estudos Avancados) - ITA (Instituto Tecnologico de Aeronautica). (author)
Theoretical Study on Sers of Wagging Vibrations of Benzyl Radical Adsorbed on Silver Electrodes
Wu, De-Yin; Chen, Yan-Li; Tian, Zhong-Qun
2016-06-01
Electrochemical surface-enhanced Raman spectroscopy (EC-SERS) has been used to characterize adsorbed species widely but reaction intermediates rarely on electrodes. In previous studies, the observed SERS signals were proposed from surface benzyl species due to the electrochemical reduction of benzyl chloride on silver electrode surfaces. In this work, we reinvestigated the vibrational assignments of benzyl chloride and benzyl radical as the reaction intermediate. On the basis of density functional theoretical (DFT) calculations and normal mode analysis, our systematical results provide more reasonable new assignments for both surface species. Further, we investigated adsorption configurations, binding energies, and vibrational frequency shifts of benzyl radical interacting with silver. Our calculated results show that the wagging vibration displays significant vibrational frequency shift, strong coupling with some intramolecular modes in the phenyl ring, and significant changes in intensity of Raman signals. The study also provides absolute Raman intensity in benzyl halides and discuss the enhancement effect mainly due to the binding interaction with respect to free benzyl radical.
Energy Technology Data Exchange (ETDEWEB)
Macia, R.; Correig, A.M.
1987-01-01
The medium through which seismic waves propagate acts as a filter. This filter is characterized by the medium spectral transfer functions, that deppend only on the model parameters that represents the medium. The behaviour of the ratio of amplitudes between spectral transfer functions, corresponding to vertical and horizontal desplacements of long period P-waves propagating though a stratified media, is analysed. Correlations between the properties of a theoretical model with respect to the curve defined by the ratio of the spectral transfer functions are studied as a function of frequency, as well as the influence of the parameters that define de model of the curves. Finally, the obtained correlations are analysed from the point of view of the utilisations to the study of the Earth's Crust. (Author)
Directory of Open Access Journals (Sweden)
Cali F. Bartholomeusz
2012-01-01
Full Text Available Improving functional outcome, in addition to alleviating psychotic symptoms, is now a major treatment objective in schizophrenia research. Given the large body of evidence suggesting pharmacological treatments generally have minimal effects on indices of functioning, research has turned to psychosocial rehabilitation programs. Among these, neurocognitive and social cognitive interventions are at the forefront of this field and are argued to target core deficits inherent to the schizophrenia illness. However, to date, research trials have primarily focused on chronic schizophrenia populations, neglecting the early psychosis groups who are often as severely impaired in social and occupational functioning. This theoretical paper will outline the rationale for investigating adjunctive cognitive-based interventions in the early phases of psychotic illness, critically examine the current approach strategies used in these interventions, and assess the evidence supporting certain training programs for improving functional outcome in early psychosis. Potential pathways for future research will be discussed.
Theoretical method for determining the three-particle distribution function of classical systems
Energy Technology Data Exchange (ETDEWEB)
Johnson, E.
1979-01-01
Equilibrium statistical mechanics is considered. A method that should yield accurate three-particle distribution functions is presented. None of the current methods is successful. It appears that the new equation presented may be used with the first and second equations in the YBG hierarchy to obtain exact single-particle, pair, and triplet distribution functions. It should be easy to generalize the results to the n-particle distribution function.
Sneck, Sami; Saarnio, Reetta; Isola, Arja; Boigu, Risto
2016-01-01
Medication administration is an important task of registered nurses. According to previous studies, nurses lack theoretical knowledge and drug calculation skills and knowledge-based mistakes do occur in clinical practice. Finnish health care organizations started to develop a systematic verification processes for medication competence at the end of the last decade. No studies have yet been made of nurses' theoretical knowledge and drug calculation skills according to these online exams. The aim of this study was to describe the medication competence of Finnish nurses according to theoretical and drug calculation exams. A descriptive correlation design was adopted. Participants and settings All nurses who participated in the online exam in three Finnish hospitals between 1.1.2009 and 31.05.2014 were selected to the study (n=2479). Quantitative methods like Pearson's chi-squared tests, analysis of variance (ANOVA) with post hoc Tukey tests and Pearson's correlation coefficient were used to test the existence of relationships between dependent and independent variables. The majority of nurses mastered the theoretical knowledge needed in medication administration, but 5% of the nurses struggled with passing the drug calculation exam. Theoretical knowledge and drug calculation skills were better in acute care units than in the other units and younger nurses achieved better results in both exams than their older colleagues. The differences found in this study were statistically significant, but not high. Nevertheless, even the tiniest deficiency in theoretical knowledge and drug calculation skills should be focused on. It is important to identify the nurses who struggle in the exams and to plan targeted educational interventions for supporting them. The next step is to study if verification of medication competence has an effect on patient safety. Copyright © 2015 Elsevier Ltd. All rights reserved.
Theoretical study of the transverse acoustic phonons of GaSb at high pressure
Indian Academy of Sciences (India)
S Shinde; M Talati; Prafulla K Jha; S P Sanyal
2004-08-01
We have investigated the phonon dispersion curves and one-phonon density of states up to the pressure of 8 GPa using a theoretical model, namely the rigid ion model. The transverse acoustic phonons as a function of pressure have been compared with the recently measured inelastic neutron scattering data which show a strong softening near the zone boundaries. The calculated one-phonon density of states show pronounced shift in the peak positions with the increase in pressure.
Anisotropic mechanical properties and Stone-Wales defects in graphene monolayer: A theoretical study
Energy Technology Data Exchange (ETDEWEB)
Fan, B.B. [School of Materials Science and Engineering, Zhengzhou University, Henan 450001 (China); Yang, X.B. [Department of Physics, South China University of Technology, Guangzhou 510640 (China); Zhang, R., E-mail: zhangray@zzu.edu.c [School of Materials Science and Engineering, Zhengzhou University, Henan 450001 (China); Zhengzhou Institute of Aeronautical Industry Management, Henan 450046 (China)
2010-06-14
We investigate the mechanical properties of graphene monolayer via the density functional theoretical (DFT) method. We find that the strain energies are anisotropic for the graphene under large strain. We attribute the anisotropic feature to the anisotropic sp{sup 2} hybridization in the hexagonal lattice. We further identify that the formation energies of Stone-Wales (SW) defects in the graphene monolayer are determined by the defect concentration and also the direction of applied tensile strain, correlating with the anisotropic feature.
du Preez, Petro; Simmonds, Shan
2014-01-01
Theoretical ambiguities in curriculum studies result in conceptual mayhem. Accordingly, they hinder the development of the complicated conversation on curriculum as a verb. This article aims to contribute to reconceptualizing curriculum studies as a dynamic social practice that aspires to thinking and acting with intelligences and sensitivity so…
Deaf Studies: A Critique of the Predominant U.S. Theoretical Direction
Myers, Shirley Shultz; Fernandes, Jane K.
2010-01-01
The focus and concerns establishing Deaf Studies in the 1970s have rigidified into a reactive stance toward changing historical conditions and the variety of deaf lives today. This critique analyzes the theoretical foundation of this stance: a tendency to downplay established research in the field of Deaf Studies and linguistics, the employment of…
García Blanco, Sonia Maria; Pollnau, Markus; Bozhevolnyi, Sergey I.
In this paper, a theoretical study of loss compensation in long-range dielectric loaded surface plasmon waveguides (LR-DLSPPs) is presented. Although extendable to other gain materials, rare-earth doped double tungstates are used as gain material in this work. Two different structures are studied
Kruyt, N.P.; Verel, W.J.Th.
1992-01-01
A theoretical and experimental study is performed of rapid, fully developed flows of cohesionless granular materials down inclined chutes with a rough base. Two flow types are studied in detail: (1) immature sliding flow, where a stagnant zone forms on the base of the chute, and (2) fully developed
Collisions of energetic particles with atoms, molecules & solids: A theoretical study
Quashie, Edwin Exam
The detailed knowledge of the accurate ion-solid interaction is at the heart of many technological applications such as nuclear safety, applied material science, medical physics and fusion and fission applications. Its accurate evaluation poses an enormous challenge due to the need of incorporating electronic structure, bound states, size effects, basis sets, and the quantum classical aspects of the problem. Most recent approaches relying on the fitting to experimental data or phenomenological model, fail to describe the ion-solid interaction properly (see [S. N. Markin, D. Primetzhofer, M. Spitz, and P. Bauer, Phys. Rev. B 80 (2009)]) for slow ions. A general Time-Dependent Density Functional Theory (TDDFT) is used in this thesis to evaluate electron-dynamics easily. For the first time a unified theory is proposed to describe the ion-solid interaction accurately over several orders of magnitude in the ion velocities, unveiling different regimes that before were only partially seen by separate experiments and rarely by any level of existing theory. We identified an electronic stopping which in the band-regime produces a quantum friction that is nonlinear with a power-law with an exponent ˜1.5. At low velocity this nonlinear effect will provide a new impetus for experimental investigations and an improve microscopic models of electron-ion dissipative dynamics. Our study will potentially impact both the experimental and theoretical research in condensed matter. We have applied our developed theory to study stopping of H+ in Cu. The target Cu comprises complicated band structure and this system will help to understand radiation of matter, both in its experimental understanding and also in the modeling of the process, for example in the context of damped molecular dynamics for the simulation of radiation cascades. At this present stage in the field of ion-solid interactions and quantum dissipative dynamics, our findings remain very significant. The same techniques are
Theoretical study of the dual harmonic system and its application on the CSNS/RCS
Yuan, Yao-Shuo; Xu, Shou-Yan; Yuan, Yue; Wang, Sheng
2015-01-01
The dual harmonic system has been widely used in high intensity proton synchrotrons to suppress the space charge effect, as well as reduce the beam loss. To investigate the longitudinal beam dynamics in the dual rf system, the potential well, the sub-buckets in the bunch and the multi-solutions of the phase equation have been studied theoretically. Based on these theoretical studis, the optimization of bunching factor and rf voltage waveform are made for the dual harmonic rf system in the upgrade phase of the CSNS/RCS. In the optimization process, the simulation with space charge effect is done by using a newly developed code C-SCSIM.
Theoretical/Computational Studies of High-Temperature Superconductivity from Quantum Magnetism
2016-06-09
AFRL-AFOSR-VA-TR-2016-0204 Theoretical/Computational Studies of High-Temperature Superconductivity from Quantum Magnetism Jose Rodriguez CALIFORNIA...TITLE AND SUBTITLE Theoretical/Computational Studies of High-Temperature Superconductivity from Quantum Magnetism 5a. CONTRACT NUMBER 5b. GRANT...SUBJECT TERMS quantum magnetism, HTS, superconductivity 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT UU 18. NUMBER OF
Shishehchi, Sara; Rudin, Sergey; Garrett, Gregory; Wraback, Michael; Bellotti, Enrico
2013-03-01
We present a theoretical and experimental study of the subpicosecond kinetics of photo-excited carriers in the wide band gap semiconductors GaN and ZnO. In the theoretical model, interaction with a photo-excitation laser pulse is treated coherently and a generalized Monte Carlo simulation is used to account for scattering and dephasing. The scattering mechanisms included are carrier interactions with polar optical phonons and acoustic phonons, and carrier-carrier Coulomb interactions. For comparison, experimental time-resolved photoluminescence studies on GaN and ZnO samples are performed over a range of temperatures and excitation powers.
Xu, Yi-Jun; Zhang, Yong-Fan; Li, Jun-Qian
2005-09-16
[structure: see text] We predict the viability of organic cycloadditions of nitrenes onto the diamond (100) surface. This new type of surface reaction can be employed to functionalize diamond surface at low temperature, which might introduce new functionalities to the diamond surface for novel applications in a diversity of fields.