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Total Energy (total + energy)
Terms modified by Total Energy Selected AbstractsScientific Highlights from the ,k Network: Towards Atomistic Materials DesignPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 11 2006P. H. Dederichs The ,k network aims at encompassing the whole community of European groups working in the area of ab - initio materials modelling, including very many small groups and isolated researchers. Historically, the activities started in the 1980s in Trieste with the workshop series entitled "Total Energies and Forces". Since then, it has operated on the European level in various forms, with funding from various EC/EU and ESF sources, beginning more than 10 years ago with the EC's Human Capital and Mobility Programme. In that time, ,k has done much to make Europe the leading area in the world for research in atomic-scale ab - initio computer simulation of all types of materials, their structures, properties, and processes. To a large extent, this has been done by nurturing scientific excellence and collaboration in what might be called "the ,k family". The ,k Network is presently organized around 15 topical working groups. Over the years, the ,k network organized three large scale conferences in Schwäbisch Gmünd, Germany (1996, 2000, 2005), attended by hundreds of scientists from all over the world. The next ,k Conference is to be organized in Berlin in 2010. These ,k Conferences are unique events fully dedicated to the ab - initio research. In addition, the network organizes a variety of meetings and topical workshops every year. The core activities of the ,k network involve editing every two months a ,k newsletter with typically more than 100 pages, which contains a "Scientific Highlight", announcements of conferences, workshops and vacant positions, news of various ESF and EU funded networks, including reports on workshops, and abstracts of submitted papers. The ,k has its own web pages (http://psi-k.dl.ac.uk) which inform about the Network, its structure, and how to get involved in ,k activities. These web pages are also the repository of the ,k newsletters and Scientific Highlights and details about the ,k Workshops of the most recent years. The ,k mailing list contains about 1700 e-mail addresses from across the world, and all the important information about a variety of activities of the network is distributed across this list on a daily basis. The "Scientific Highlights" of the ,k newsletters reflect the scientific activities of the network and aim at presenting reviews and current developments in the field. This special issue of physica status solidi (b) gives a collection of some of the most recent Highlight contributions to the ,k newsletter. All manuscripts originally posted on the ,k server were peer-reviewed by two referees and accepted according to the standards of pss. They are published here partly in revised or updated version. We hope that the readership of the journal will benefit from the quality of the research they report on and the high level of the presentations. [source] State of the Art Simulations in Electronic Structure and Total Energy for the High Temperature Superconductor YBa2Cu3O7.CHEMINFORM, Issue 2 2006K. Larbaoui No abstract is available for this article. [source] Spin densities in two-component relativistic density functional calculations: Noncollinear versus collinear approachJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 8 2002Christoph Van WüllenArticle first published online: 3 APR 200 Abstract With present day exchange-correlation functionals, accurate results in nonrelativistic open shell density functional calculations can only be obtained if one uses functionals that do not only depend on the electron density but also on the spin density. We consider the common case where such functionals are applied in relativistic density functional calculations. In scalar-relativistic calculations, the spin density can be defined conventionally, but if spin-orbit coupling is taken into account, spin is no longer a good quantum number and it is not clear what the "spin density" is. In many applications, a fixed quantization axis is used to define the spin density ("collinear approach"), but one can also use the length of the local spin magnetization vector without any reference to an external axis ("noncollinear approach"). These two possibilities are compared in this work both by formal analysis and numerical experiments. It is shown that the (nonrelativistic) exchange-correlation functional should be invariant with respect to rotations in spin space, and this only holds for the noncollinear approach. Total energies of open shell species are higher in the collinear approach because less exchange energy is assigned to a given Kohn-Sham reference function. More importantly, the collinear approach breaks rotational symmetry, that is, in molecular calculations one may find different energies for different orientations of the molecule. Data for the first ionization potentials of Tl, Pb, element 113, and element 114, and for the orientation dependence of the total energy of I and PbF indicate that the error introduced by the collinear approximation is ,0.1 eV for valence ionization potentials, but can be much larger if highly ionized open shell states are considered. Rotational invariance is broken by the same amount. This clearly indicates that the collinear approach should not be used, as the full treatment is easily implemented and does not introduce much more computational effort. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 779,785, 2002 [source] Hydrogenation and oxygenation of the (100) diamond surface and the consequences for transfer dopingPHYSICA STATUS SOLIDI (A) APPLICATIONS AND MATERIALS SCIENCE, Issue 11 2005S. J. Sque Abstract Ab initio density-functional-theory calculations have been performed to determine the structural and electronic properties of the (100) diamond surface with various hydrogen and oxygen terminations. Total energies indicate that an ,OH-terminated surface is favoured over an oxygenated surface plus gas-phase hydrogen. Ionisation potentials and electron affinities (EAs) are reported for the different systems, and the distinction is made between bulk- and surface-related properties. A first-order correction is used to offer estimated surface EAs. A negative bulk EA is found for surfaces terminated with ,H and ,OH groups, although many surfaces have deep traps which can act as positive EA in the absence of band bending. (© 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Turkey's sectoral energy and exergy analysis between 1999 and 2000INTERNATIONAL JOURNAL OF ENERGY RESEARCH, Issue 13 2004Zafer Utlu Abstract This study analyses sectoral energy and exergy utilization in Turkey between 1999 and 2000. Total energy and exergy utilization efficiencies are calculated to be 43.24 and 24.04% in 1999, and 44.91 and 24.78% in 2000, respectively. In order to calculate these efficiency values, Turkey is subgrouped into four main sectors, namely utility, industrial, transportation and commercial-residential. The energy efficiency values are found to be 23.88, 30.10, 68.97 and 57.76% in 1999, and 23.71, 30.11, 68.81 and 57.05% in 2000 for transportation, utility, industrial and commercial-residential sectors, respectively. Besides this, the exergy efficiency values are obtained to be 23.80, 30.28, 35.97 and 8.12% in 1999, and 23.65, 30.47, 35.51 and 8.02% in 2000 for the same order of sectors. The present study has clearly shown the necessity of the planned studies towards increasing exergy efficiencies in the sectors studied. Copyright © 2004 John Wiley & Sons, Ltd. [source] FOOD HARDNESS AND FRACTURABILITY ASSESSMENT BY AN ELECTRONIC SENSING SYSTEM1JOURNAL OF TEXTURE STUDIES, Issue 2 2002YANKUN PENG ABSTRACT Two texture properties of food, hardness and fracturability, were studied by an electronic sensing system (ESS) with 29 cereal-based foods that represented a range of textures. Three electrodes were used with one located on the cheekbone, one on the lower jaw bone, and the other one, a ground, on the ear lobe. Total energy, peak energy, and Fourier power of the first bite ESS signals were analyzed. The Fourier power of the muscle motion in biting was highly correlated to the muscle motion total energy. Sensory hardness and fracturability were correlated with the first bite ESS total energy and first bite ESS Fourier power (r = 0.82 and 0.74). [source] Quantum chemical metabolism-based simulation of carcinogenic potency of benzene derivativesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 7 2010Pavel N. D'Yachkov Abstract Using an oxenoid model, we investigated dependences of carcinogenic potency of the benzenes C6H5 -X on a nature of substituents X. According to the model, a P450 enzyme breaks a dioxygen molecule and generates the oxens, which readily react with substrates. We suggest that a stability of the intermediate OC6H6 -X with tetrahedrally coordinated C atom relative to the molecule C6H5 -X determines a rate of substrate biotransformation. Using MO LCAO MNDO approach, we calculated the total energies of molecules C6H6 -X and arene oxides OC6H6 -X. A difference ,Emin of these values determines activation energy of oxidation reaction. The compounds with the low ,Emin values are noncarcinogenic. Benzene derivatives with high ,Emin values belong to carcinogenic compounds series. The carcinogenicity of amino- and nitro-substituted benzenes is also determined by N-oxidation of amino and reduction of the nitro group. As the phenylhydroxylamines XC6H4NHOH and nitrenium ions XC6OH4NH+ are the common metabolites of the nitro- and amino-substituted benzenes and nitrenium ions XC6H4NH+ are the ultimate carcinogens, we use the differences ,EN = E(XC6H4NH+) , E(XC6H4NHOH) as the second parameter characterizing the carcinogenic activity of amino- and nitro-substituted benzenes. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] Hydrogen bonding interaction between 1,4-dioxane and waterINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2010Ajay Chaudhari Abstract This work reports an interaction of 1,4-dioxane with one, two, and three water molecules using the density functional theory method at B3LYP/6-311++G* level. Different conformers were studied and the most stable conformer of 1,4-dioxane-(water)n (n = 1,3) complex has total energies ,384.1964038, ,460.6570694, and ,537.1032381 hartrees with one, two, and three water molecules, respectively. Corresponding binding energy (BE) for these three most stable structures is 6.23, 16.73, and 18.11 kcal/mol. The hydrogen bonding results in red shift in OO stretching and CC stretching modes of 1,4-dioxane for the most stable conformer of 1,4-dioxane with one, two, and three water molecules whereas there was a blue shift in CO symmetric stretching and CO asymmetric stretching modes of 1,4-dioxane. The hydrogen bonding results in large red shift in bending mode of water and large blue shift in symmetric stretching and asymmetric stretching mode of water. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [source] Grid-based density functional calculations of many-electron systemsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2008Amlan K. RoyArticle first published online: 10 DEC 200 Abstract Exploratory variational pseudopotential density functional calculations are performed for the electronic properties of many-electron systems in the 3D cartesian coordinate grid (CCG). The atom-centered localized gaussian basis set, electronic density, and the two-body potentials are set up in the 3D cubic box. The classical Hartree potential is calculated accurately and efficiently through a Fourier convolution technique. As a first step, simple local density functionals of homogeneous electron gas are used for the exchange-correlation potential, while Hay-Wadt-type effective core potentials are employed to eliminate the core electrons. No auxiliary basis set is invoked. Preliminary illustrative calculations on total energies, individual energy components, eigenvalues, potential energy curves, ionization energies, and atomization energies of a set of 12 molecules show excellent agreement with the corresponding reference values of atom-centered grid as well as the grid-free calculation. Results for three atoms are also given. Combination of CCG and the convolution procedure used for classical Coulomb potential can provide reasonably accurate and reliable results for many-electron systems. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2008 [source] Model density approach to the Kohn,Sham problem: Efficient extension of the density fitting techniqueINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 5 2005Uwe Birkenheuer Abstract We present a novel procedure for treating the exchange-correlation contributions in the Kohn,Sham procedure. The approach proposed is fully variational and closely related to the so-called "fitting functions" method for the Coulomb Hartree problem; in fact, the method consistently uses this auxiliary representation of the electron density to determine the exchange-correlation contributions. The exchange-correlation potential and its matrix elements in a basis set of localized (atomic) orbitals can be evaluated by reusing the three-center Coulomb integrals involving fitting functions, while the computational cost of the remaining numerical integration is significantly reduced and scales only linearly with the size of the auxiliary basis. We tested the approach extensively for a large set of atoms and small molecules as well as for transition-metal carbonyls and clusters, by comparing total energies, atomization energies, structure parameters, and vibrational frequencies at the local density approximation and generalized gradient approximation levels of theory. The method requires a sufficiently flexible auxiliary basis set. We propose a minimal extension of the conventional auxiliary basis set, which yields essentially the same accuracy for the quantities just mentioned as the standard approach. The new method allows one to achieve substantial savings compared with a fully numerical integration of the exchange-correlation contributions. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 [source] Theoretical investigation of an energetic fullerene derivativeJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 12 2010Bisheng Tan Abstract A self-consistent estimation method for the thermochemical properties of N -methyl-3-(2,,4,,6,-trinitrobenzene)-fulleropyrrolidine (MTNBFP) is presented. This method is based on enthalpy of formation (,fH) and enthalpy of combustion obtained from BLYP/DNP calculations of the total energies and frequencies for MTNBFP. The enthalpy of formation was calculated by an optimized set of isodesmic reactions given the available experimental ,fH of relative compounds. MTNBFP has a high enthalpy of formation, 2782.2 kJ/mol. Detonation velocity and detonation pressure were also presented in terms of Kamlet and Jacobs equations. Drop hammer impact sensitivity tests and blasting point per 5 s tests indicate MTNBFP may be a potential candidate primary explosive. To understand the test results well, we proposed a series of chemical reaction mechanisms and interpreted the relationship between impact sensitivity and electronic structures from the viewpoint of nitro group charge, electrostatic potential, and vibrational modes. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010 [source] Hartree,Fock exchange fitting basis sets for H to Rn ,JOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 2 2008Florian Weigend Abstract For elements H to Rn (except Lanthanides), a series of auxiliary basis sets fitting exchange and also Coulomb potentials in Hartree,Fock treatments (RI-JK-HF) is presented. A large set of small molecules representing nearly each element in all its common oxidation states was used to assess the quality of these auxiliary bases. For orbital basis sets of triple zeta valence and quadruple zeta valence quality, errors in total energies arising from the RI-JK approximation are below ,1 meV per atom in molecular compounds. Accuracy of RI-JK-approximated HF wave functions is sufficient for being used for post-HF treatments like Møller,Plesset perturbation theory, MP2. Compared to nonapproximated treatments, RI-JK-HF leads to large computational savings for quadruple zeta valence orbital bases and, in case of small to midsize systems, to significant savings for triple zeta valence bases. © 2007 Wiley Periodicals, Inc. J Comput Chem, 2008 [source] Spin states in polynuclear clusters: The [Fe2O2] core of the methane monooxygenase active siteJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 12 2006Carmen Herrmann Abstract The ability to provide a correct description of different spin states of mono- and polynuclear transition metal complexes is essential for a detailed investigation of reactions that are catalyzed by such complexes. We study the energetics of different total and local spin states of a dinuclear oxygen-bridged iron(IV) model for the intermediate Q of the hydroxylase component of methane monooxygenase by means of spin-unrestricted Kohn,Sham density functional theory. Because it is known that the spin state total energies depend systematically on the density functional, and that this dependence is intimately connected to the exact exchange admixture of present-day hybdrid functionals, we compare total energies, local and total spin values, and Heisenberg coupling constants calculated with the established functionals BP86 and B3LYP as well as with a modified B3LYP version with an exact exchange admixture ranging from 0 to 24%. It is found that exact exchange enhances local spin polarization. As the exact exchange admixture increases, the high-spin state is energetically favored, although the Broken-Symmetry state always is the ground state. Instead of the strict linear variation of the energy splittings observed for mononuclear complexes, a slightly nonlinear dependence is found. The Heisenberg coupling constants JFe1Fe2,evaluated according to three different proposals from the literature,are found to vary from ,129 to ,494cm,1 accordingly. The experimental finding that intermediate Q has an antiferromagnetic ground state is thus confirmed. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 1223,1239, 2006 [source] Structures and energies of D -galactose and galabiose conformers as calculated by ab initio and semiempirical methodsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 7 2003Majda Rahal-Sekkal Abstract Optimized geometries and total energies of some conformers of ,- and ,- D -galactose have been calculated using the RHF/6-31G* ab initio method. Vibrational frequencies were computed at the 6-31G* level for the conformers that favor internal hydrogen bonding, in order to evaluate their enthalpies, entropies, Gibbs free energies, and then their structural stabilities. The semiempirical AM1, PM3, MNDO methods have also been performed on the conformers GG, GT, and TG of ,- and ,- D -galactose. In order to test the reliability of each semiempirical method, the obtained structures and energies from the AM1, PM3, and MNDO methods have been compared to those achieved using the RHF/6-31G* ab initio method. The MNDO method has not been investigated further, because of the large deviation in the structural parameters compared with those obtained by the ab initio method for the galactose. The semiempirical method that has yielded the best results is AM1, and it has been chosen to perform structural and energy calculations on the galabiose molecule (the disaccharides constituted by two galactose units , 1,4 linked). The goal of such calculations is to draw the energy surface maps for this disaccharide. To realize each map, 144 different possible conformations resulting from the rotations of the two torsional angles , and , of the glycosidic linkage are considered. In each calculation, at each increment of , and ,, using a step of 30° from 0 to 330°, the energy optimization is employed. In this article, we report also calculations concerning the galabiose molecule using different ab initio levels such as RHF/6-31G*, RHF/6-31G**, and B3Lyp/6-31G*. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 806,818, 2003 [source] Parallelization of multireference perturbation calculations with GAMESSJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 12 2001Hiroaki Umeda Abstract The quasi-degenerate multireference second-order perturbation theory (MRMP2) routines in the GAMESS suite of program codes have been parallelized using a distributed data interface (DDI). Two typical kinds of molecules were chosen for examination of parallelization speedup using one to eight PCs gathered as a cluster and connected by Fast Ethernet. The first example, in which total energies of several low-lying electronic states have been obtained for niobium monohydride, give parallelization speedup of 7.15 when eight PCs were used as a cluster. The second example is the ground-state total energy for a medium sized molecule, 4a,4b,8a,9a-tetrahydro-pyridino[1,,2,-4,3]imidazo-lidino[1,5-a]pyridine. When distributed memory is employed, the parallelization speedup improves to 6.84 for the MRMP2 calculations when an eight-PC cluster is used. These results demonstrate that our efforts to achieve the parallelization of MRMP2 routines have been successful. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1243,1251, 2001 [source] Calculation of XANES/ELNES Spectra of All Edges in Si3N4 and Si2N2OJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 1 2002Wai-Yim Ching Using a recently developed first-principles supercell method that includes the electron and core-hole interaction, the XANES/ELNES spectra of Si- L2,3, Si- K, and N- K edges in ,-Si3N4, ,-Si3N4, spinel c -Si3N4, and Si2N2O were calculated and compared. The difference in total energies between the initial ground state and the final core-hole state provides the transition energy. The calculated spectra are found to be in good agreement with the experimental measurements on ,-Si3N4 and c -Si3N4. The differences in the XANES/ELNES spectra for the same element in different crystals are explained in terms of differences in local bonding. The use of orbital-decomposed local density of states to explain the measured spectra is shown to be inadequate. These results reaffirm the importance of including the core-hole effect in any XANES/ELNES spectral calculation. [source] Computational methods for studies of multiexciton complexes,PHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 15 2006T. Vänskä Abstract Powerful computational methods are presented for studies of energy levels, photon-recombination rates, and phonon-relaxation rates of neutral and charged multiexciton complexes at correlated levels of theory. The electron,hole system is described by a two-band effective-mass Hamiltonian. The one-particle functions are expanded in a basis set consisting of anisotropic Gaussian functions. The many-body Hamiltonian constructed in the space of the antisymmetric products of one-particle functions is diagonalized using general coupled-cluster and configuration-interaction methods. The expansion coefficients of the coupled-cluster and configuration-interaction wave functions are obtained by solving the corresponding equations using direct iterative algorithms. We demonstrate the potential of the computational approaches by calculating total energies of multiexciton complexes at coupled-cluster and configuration-interaction levels. Computational methods for studies of radiative recombination and phonon-relaxation rates have also been developed and results are reported for radiative recombination rates and recombination energies of the exciton, biexciton, and of the positive and the negative trions confined in a InGaAs/GaAs quantum-dot sample. Phonon-relaxation rates have been calculated for a few low-lying ,g states of the exciton complex of the same quantum-dot sample. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Formation of iminium ions by fragmentation of a2 ionsRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 14 2004Alex G. Harrison Tandem mass spectrometric experiments have been carried out on the protonated amides H-Gly-Ala-NH2, H-Ala-Gly-NH2, H-Ala-Val-NH2, H-Val-Ala-pNA, H-Leu-Phe-NH2, H-Phe-Leu-NH2, H-Phe-Tyr-NH2 and H-Tyr-Phe-NH2 with particular emphasis on the fragmentation of the isomeric a2 ions derived therefrom. Primary fragmentation reactions of the protonated amides involve formation of the y1, and b2 ions with further fragmentation of the b2 ion to form the a2 ion which fragments to form iminium ions. Collision-induced dissociation studies of the mass-selected a2 ions were carried out. For the Gly-Ala, Ala-Gly and Val-Ala a2 ions, weak signals were observed corresponding to loss of CO from the a2 ion. With the exception of the Gly-Ala, Ala-Gly and Val-Ala a2 ions, both possible iminium ions (a1 and the internal iminium ion) are observed with the most abundant being that formed by proton attachment to the imine of higher proton affinity. The results provide strong support for the recently proposed (El Aribi et al. J. Am. Chem. Soc. 2003; 125: 9229) mechanism of fragmentation of a2 ions which involves elimination of CO from the a2 ion to form a proton-bound complex of two imines. Based on this mechanism ab initio calculations of the total energies of the a2 ions and the transition states for fragmentation have been carried out giving the energy barrier for fragmentation of each a2 ion. The experimental results are interpreted in terms of these energetics data, unimolecular rate constants calculated by using the RRKM theory, and the imine proton affinities. Copyright © 2004 John Wiley & Sons, Ltd. [source] Turbulence energetics in stably stratified geophysical flows: Strong and weak mixing regimesTHE QUARTERLY JOURNAL OF THE ROYAL METEOROLOGICAL SOCIETY, Issue 633 2008S. S. Zilitinkevich Abstract Traditionally, turbulence energetics is characterised by turbulent kinetic energy (TKE) and modelled using solely the TKE budget equation. In stable stratification, TKE is generated by the velocity shear and expended through viscous dissipation and work against buoyancy forces. The effect of stratification is characterised by the ratio of the buoyancy gradient to squared shear, called the Richardson number, Ri. It is widely believed that at Ri exceeding a critical value, Ric, local shear cannot maintain turbulence, and the flow becomes laminar. We revise this concept by extending the energy analysis to turbulent potential and total energies (TPE, and TTE = TKE + TPE), consider their budget equations, and conclude that TTE is a conservative parameter maintained by shear in any stratification. Hence there is no ,energetics Ric', in contrast to the hydrodynamic-instability threshold, Ric,instability, whose typical values vary from 0.25 to 1. We demonstrate that this interval, 0.25 < Ri < 1, separates two different turbulent regimes: strong mixing and weak mixing rather than the turbulent and the laminar regimes, as the classical concept states. This explains persistent occurrence of turbulence in the free atmosphere and deep ocean at Ri , 1, clarifies the principal difference between turbulent boundary layers and free flows, and provides the basis for improving operational turbulence closure models. Copyright © 2008 Royal Meteorological Society [source] The lines-of-force landscape of interactions between molecules in crystals; cohesive versus tolerant and `collateral damage' contactACTA CRYSTALLOGRAPHICA SECTION B, Issue 3 2010Angelo Gavezzotti A quantitative analysis of relative stabilities in organic crystal structures is possible by means of reliable calculations of interaction energies between pairs of molecules. Such calculations have been performed by the PIXEL method for 1108 non-ionic and 98 ionic organic crystals, yielding total energies and separate Coulombic polarization and dispersive contributions. A classification of molecule,molecule interactions emerges based on pair energy and its first derivative, the interaction force, which is estimated here explicitly along an approximate stretching path. When molecular separation is not at the minimum-energy value, as frequently happens, forces may be attractive or repulsive. This information provides a fine structural fingerprint and may be relevant to the mechanical properties of materials. The calculations show that the first coordination shell includes destabilizing contacts in ,,9% of crystal structures for compounds with highly polar chemical groups (e.g. CN, NO2, SO2). Calculations also show many pair contacts with weakly stabilizing (neutral) energies; such fine modulation is presumably what makes crystal structure prediction so difficult. Ionic organic salts or zwitterions, including small peptides, show a Madelung-mode pairing of opposite ions where the total lattice energy is stabilized from sums of strongly repulsive and strongly attractive interactions. No obvious relationships between atom,atom distances and interaction energies emerge, so analyses of crystal packing in terms of geometrical parameters alone should be conducted with due care. [source] What Does the Conservation of Energy Have to Do with Physicalism?DIALECTICA, Issue 4 2006Barbara Montero The conservation of energy law, a law of physics that states that the total energy of any closed system is always conserved, is a bedrock principle that has achieved both broad theoretical and experimental support. Yet if interactive dualism is correct, it is thought that the mind can affect physical objects in violation of the conservation of energy. Thus, some claim, the conservation of energy grounds an argument for physicalism. Although critics of the argument focus on the implausibility of causation requiring the transference of energy, I argue that even if causation requires the transference of energy, once we accept the other required premises of the argument that lie behind any supposed argument from the conservation of energy the law of the conservation of energy is revealed as irrelevant to the question of whether the mental is physical. [source] Radical Cation and Dication Derived from 4,8-Diethylbenzo[1,2- d:4,5- d,]bis[1,2,3]trithiole [DEBBT]: Change of Electronic State from Singlet-State Dication DEBBT(2+)- S to Triplet-State Dimer 2DEBBT(2+)- T in D2SO4 and CD3CN SolutionsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 24 2003Takeshi Kimura Abstract 4,8-Diethylbenzo[1,2- d:4,5- d,]bis[1,2,3]trithiole [DEBBT] was oxidized using concentrated D2SO4, leading to the generation of the radical cation DEBBT(·+) which was verified by ESR spectroscopy. DEBBT(·+) in the solution was further oxidized to produce the dication DEBBT(2+), as determined by 1H and 13C NMR spectroscopy. DEBBT(2+) was also prepared by treating DEBBT 1-oxide [DEBBT 1-O] with concentrated D2SO4, and was verified by 1H and 13C NMR spectroscopy. The 13C NMR chemical shifts of DEBBT(2+), calculated by the density functional theoretical (DFT) method at the B3LYP6-31G** level, correlated well with those obtained experimentally. The ESR signal of DEBBT(2+) generated from DEBBT 1-O was observed in solution, which implies that the singlet-state dication DEBBT(2+)- S isomerizes to the triplet-state dication DEBBT(2+)- T, and that two molecules of DEBBT(2+)- T further form a spin pair at one trithiole ring with significant distance between the two radical centers. The oxidation of DEBBT with one or two equivalents of single-electron oxidizing reagents produced DEBBT(·+) and DEBBT(2+), and the salts were isolated in a stable form. However, the DEBBT(2+) that was prepared by oxidation with NOPF6 proved silent for NMR in CD3CN, while ESR was active. The stability, electronic state, and NMR and ESR spectroscopy of the dication are affected by solvation with D2SO4 and CD3CN. The optimized structures and the total energy of the singlet- and triplet-state dication were calculated using the DFT method at the B3LYP6-31G** level, which shows that the structures of the singlet- and triplet-state dications have a completely planar form with 1.7 kcal/mol as the total energy difference between them. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Enhancement of fracture toughness due to energy screening effectin the early stages of non-elastic failureFATIGUE & FRACTURE OF ENGINEERING MATERIALS AND STRUCTURES, Issue 8 2003M. P. WNUK ABSTRACT A triaxiality-dependent cohesive zone model for a stationary and a quasistatic crack is proposed. The model is rooted in the mesomechanical approach to Fracture Mechanics and is inspired by the quantum law concerning emission of light, which was postulated by Max Planck at the end of the 19th century. The model provides an extension of the early concepts of Barenblatt, Dugdale and the Bilby,Cotrell,Swinden team. It also incorporates the experimental observations of the pre-fracture states due to Panin and his school in Tomsk. Relations between micro- and macroparameters that characterize the deformation and fracture processes in dissipative media are described in detail. The analysis suggests that the ratio of the ,true' work of fracture to the total energy dissipated during the course of the irreversible deformation contained within the end zone can be used as a measure of material resistance to a quasistatically propagating fracture. [source] Vertical (La,Sr)MnO3 Nanorods from Track-Etched Polymers Directly Buffering SubstratesADVANCED FUNCTIONAL MATERIALS, Issue 6 2010Adrián Carretero-Genevrier Abstract A novel and general methodology for preparing vertical, complex-oxide nanostructures from a sol,gel-based polymer-precursor solutions is developed using track-etched polymers directly buffering substrates. This method is able to develop a nanostructure over the entire substrate, the dimensions and localization of the vertical nanostructures being preset by the polymeric nanotemplate. Thereby, nanostructures with lateral sizes in the range of 100 to 300,nm and up to 500,nm in height have been grown. Two examples are presented herein, the latter being the evolution of the initial, metastable nanostructure. Specifically, La0.7Sr0.3MnO3 polycrystalline rods are grown at mild temperatures (800,°C); upon strong thermal activation (1000,°C) they suffer a profound transformation into vertical, single-crystalline (La,Sr)xOy nanopyramids sitting on a La0.7Sr0.3MnO3 epitaxial wetting layer. The driving force for this outstanding nanostructural evolution is the minimization of the total energy of the system, which is reached by reducing the grain-boundary, total-surface, and strain-relaxation energies. Finally, advanced electron-microscopy techniques are used to highlight the complex phase separation and structural transformations occurring when the metastable state is overcome. [source] Energy distribution of the universe in the Bianchi type II cosmological modelsFORTSCHRITTE DER PHYSIK/PROGRESS OF PHYSICS, Issue 4 2006O. Aydogdu Abstract Using the energy-momentum complexes of Tolman, Papapetrou and Weinberg, the total energy of the universe in Locally Rotationally Symmetric (LRS) Bianchi type II models is calculated. The total energy is found to be zero due to the matter plus field. This result supports the viewpoint of Tryon, Rosen and Albrow. [source] Discrete Bose-Einstein systems in a box with low adiabatic invariantFORTSCHRITTE DER PHYSIK/PROGRESS OF PHYSICS, Issue 4-5 2003V.I. Vlad The Bose-Einstein energy spectrum of an ideal quantum gas confined in a box is discrete and strongly dependent on the box geometry and temperature, for low product of the atomic mass number, Aat and the adiabatic invariant, TV2/3, i.e. on , = Aat TV2/3. Even within the approximation of non-interacting particles in the gas, the calculation of the thermodynamic properties of Bose-Einstein systems turns out to be a difficult mathematical problem. The present study compares the total number of particles, the total energy and the specific heat obtained by sums over the discrete states to the results of the approximate integrals (for defined values of ,) and shows the noticeable errors of the last ones at low adiabatic invariant (around condensation). Then, more rigorous and precise analytical approximations of sums are found in the case of finite number of atoms (correlated with the existence of a zero energy level) and the finite volume of the gas. The corrected thermodynamic functions depend on , (for fixed fugacity). The condensation temperature is corrected also in order to describe more accurately the discrete Bose-Einstein systems. Under these circumstances, the analysis of the specific heat leads to the conclusion that it shows no discontinuity, for the entire range of , values. [source] Dialysis adequacy and nutritional status of hemodialysis patientsHEMODIALYSIS INTERNATIONAL, Issue 1 2008Fernanda TEIXEIRA NUNES Abstract To characterize the nutritional status of renal failure patients and its relationship with hemodialysis adequacy measured by Kt/V, a study was carried out with a population of 44 adult patients with renal failure and mean age 51±15 years. Anthropometric data, such as dry weight, height, arm circumference, triceps skinfold thickness, mid-arm muscle circumference, and body mass index were assessed, and biochemical tests were conducted for urea, potassium, creatinine, serum albumin, and phosphorus levels, in addition to hemogram and quarterly urea reduction rate average (Kt/V). In order to evaluate calorie intake, a dietary questionnaire on habitual daily food ingestion was administered, taking into consideration the hemodialysis date. The patients were divided into 2 separate groups for the statistical analysis, with 50% of the patients in each group: A (Kt/V<1.2) and B (Kt/V>1.2). The data were tabulated as mean and standard deviation, with differences tested by Student's t test. The correlations between variables were established by the coefficient p of Pearson. Most of the patients (43%) were considered eutrophic, based on the BMI, and presented inadequate calorie intake, corresponding to 88.5±24% (30.8 kcal/kg actual weight) of the total energy required and adequate protein intake, reaching 109.9±40% of the recommended daily allowance (1.24 g/kg of actual weight). There was a correlation of Kt/V with anthropometric parameters such as body mass index, arm circumference, and mid-arm muscle circumference. The biochemical parameters related to dialysis adequacy were albumin, ferritin, and urea (predialysis). Well-dialyzed patients presented better levels of serum albumin. There was an influence of gender and age on correlations of the analyzed variables. Female and younger patients presented better dialysis adequacy. The dialysis adequacy was related to the nutritional status and influenced by the protein intake and body composition. Gender and age had an important influence in the dialysis adequacy, as men presented lower dialysis adequacy and younger adults presented better dialysis adequacy. Further research is necessary to understand better how to facilitate effective and efficient techniques for the nutritional status assessment of hemodialysis patients. [source] Effect of Er:YAG laser and EDTAC on the adhesiveness to dentine of different sealers containing calcium hydroxideINTERNATIONAL ENDODONTIC JOURNAL, Issue 7 2003F. Picoli Abstract Aim, To evaluate the effect of 15% EDTAC solution and Er:YAG laser irradiation on the adhesiveness to dentine of root canal sealers containing calcium hydroxide. Methodology, The crowns of 60 maxillary human molars were ground until dentine was exposed. The teeth were divided into three groups of 20 teeth: group I, the dentine surface received no treatment; group II, 15% EDTAC solution was applied to the dentine; group III, the dentine received Er:YAG laser application (11 mm focal distance with perpendicular incidence to dentine surface; 4 Hz frequency; 200 mJ energy; 2.25 W potency; 62 J total energy; 1 min application time). Aluminium cylinders filled with the sealers, Sealer 26, Apexit, Sealapex and CRCS, were then applied to the treated surfaces. Adhesiveness was measured with a universal testing machine, with traction results given in MegaPascals (MPa). These results were submitted to anova tests. Results, Statistical analysis showed significant differences (P < 0.01) amongst adhesiveness values of the sealers and treatments tested. Thus, sealers could be ranked in decreasing adhesiveness values: Sealer 26, CRCS, Apexit, Sealapex. Er:YAG laser irradiation and EDTAC solution application increased adhesiveness values only for Sealer 26 and Apexit. Laser irradiation was superior to EDTAC application only for Sealer 26 adhesiveness values. Conclusions, Er:YAG laser is as efficient as EDTAC solution in increasing adhesiveness of root canal sealers containing calcium hydroxide to human dentine. [source] A continuum-to-atomistic bridging domain method for composite latticesINTERNATIONAL JOURNAL FOR NUMERICAL METHODS IN ENGINEERING, Issue 13 2010Mei Xu Abstract The bridging domain method is an overlapping domain decomposition approach for coupling finite element continuum models and molecular mechanics models. In this method, the total energy is decomposed into atomistic and continuum parts by complementary weight functions applied to each part of the energy in the coupling domain. To enforce compatibility, the motions of the coupled atoms are constrained by the continuum displacement field using Lagrange multipliers. For composite lattices, this approach is suboptimal because the internal modes of the lattice are suppressed by the homogeneous continuum displacement field in the coupling region. To overcome this difficulty, we present a relaxed bridging domain method. In this method, the atom set is divided into primary and secondary atoms; the relative motions between them are often called the internal modes. Only the primary atoms are constrained in the coupling region, which succeed in allowing these internal modes to fully relax. Several one- and two-dimensional examples are presented, which demonstrate improved accuracy over the standard bridging domain method. Copyright © 2009 John Wiley & Sons, Ltd. [source] Energy,momentum consistent finite element discretization of dynamic finite viscoelasticityINTERNATIONAL JOURNAL FOR NUMERICAL METHODS IN ENGINEERING, Issue 11 2010M. Groß Abstract This paper is concerned with energy,momentum consistent time discretizations of dynamic finite viscoelasticity. Energy consistency means that the total energy is conserved or dissipated by the fully discretized system in agreement with the laws of thermodynamics. The discretization is energy,momentum consistent if also momentum maps are conserved when group motions are superimposed to deformations. The performed approximation is based on a three-field formulation, in which the deformation field, the velocity field and a strain-like viscous internal variable field are treated as independent quantities. The new non-linear viscous evolution equation satisfies a non-negative viscous dissipation not only in the continuous case, but also in the fully discretized system. The initial boundary value problem is discretized by using finite elements in space and time. Thereby, the temporal approximation is performed prior to the spatial approximation in order to preserve the stress objectivity for finite rotation increments (incremental objectivity). Although the present approach makes possible to design schemes of arbitrary order, the focus is on finite elements relying on linear Lagrange polynomials for the sake of clearness. The discrete energy,momentum consistency is based on the collocation property and an enhanced second Piola,Kirchhoff stress tensor. The obtained coupled non-linear algebraic equations are consistently linearized. The corresponding iterative solution procedure is associated with newly proposed convergence criteria, which take the discrete energy consistency into account. The iterative solution procedure is therefore not complicated by different scalings in the independent variables, since the motion of the element is taken into account for solving the viscous evolution equation. Representative numerical simulations with various boundary conditions show the superior stability of the new time-integration algorithm in comparison with the ordinary midpoint rule. Both the quasi-rigid deformations during a free flight, and large deformations arising in a dynamic tensile test are considered. Copyright © 2009 John Wiley & Sons, Ltd. [source] | |||||||||||||||||||||||||||||||