Effective t-J model Hamiltonian parameters of monolayered cuprate superconductors from ab initio electronic structure calculations

The magnetic coupling constant of selected cuprate superconductor parent compounds has been determined by means of embedded cluster model and periodic calculations carried out at the same level of theory. The agreement between both approaches validates the cluster model. This model is subsequently employed in state-of-the-art configuration interaction calculations aimed to obtain accurate values of the magnetic coupling constant and hopping integral for a series of superconducting cuprates. Likewise, a systematic study of the performance of different ab initio explicitly correlated wave function methods and of several density functional approaches is presented. The accurate determination of the parameters of the t-J Hamiltonian has several consequences. First, it suggests that the appearance of high-Tc superconductivity in existing monolayered cuprates occurs with J/t in the 0.20¿0.35 regime. Second, J/t=0.20 is predicted to be the threshold for the existence of superconductivity and, third, a simple and accurate relationship between the critical temperatures at optimum doping and these parameters is found. However, this quantitative electronic structure versus Tc relationship is only found when both J and t are obtained at the most accurate level of theory.

Ferromagnetic instabilities in neutron matter at finite temperature with the Skyrme interaction

The properties of spin-polarized neutron matter are studied at both zero and finite temperature using Skyrme-type interactions. It is shown that the critical density at which ferromagnetism takes place decreases with temperature. This unexpected behavior is associated to an anomalous behavior of the entropy that becomes larger for the polarized phase than for the unpolarized one above a certain critical density. This fact is a consequence of the dependence of the entropy on the effective mass of the neutrons with different third spin component. A new constraint on the parameters of the effective Skyrme force is derived if this behavior is to be avoided.

A REVIEW OF SOIL CONSTITUTIVE MODELS FOR SOIL STRUCTURE INTEREACTION ANALYSIS

Soils are multiphase materials comprised of mineral grains, air voids and water. Soils are not linearly elastic or perfectly plastic for external loading. Various constitutive models are available to describe the various aspects of soil behaviour. But no single soil model can completely describe the behaviour of real soil under all conditions. This paper attempts to compare various soil models and suggest a suitable model for the Soil Structure Interaction analysis especially for Kochi marine clay.

Species diversity and community structure of ichthyofauna in the seagrass ecosystem of Minicoy Atoll, Lakshadweep, India

Present study consists the species diversity, abundance and community structure of ichthyofauna in the seagrass meadow of Minicoy Atoll, Lakshadweep Islands. Two hundred and three species of fishes were recorded during the study, from four stations in the Atoll. They belonged to 2 classes, 11orders, 43 families and 93 genera. Six species belonged to the class Chondreichthyes and 197 species to Osteichthyes. Family Pomacentridae showed maximum abundance of species (22%). Station I, having close proximity to the coral reefs, observed the maximum number of families (37) and species (129) and that with minimum number was in station II (23 families and 52 species). Bray-Curtis similarity plot showed a similarity range of 22 to 52%, seasonally. Station I showed highest Shannon-Wiener diversity index (H’log2) (4.22) during August and the lowest (2.91) during June. Stations I and III showed comparatively higher abundance and diversity of fishes. Variability in seagrass habitat structure and the interaction with coral reefs influenced the species composition and diversity of fishes in Minicoy Atoll. The findings of the present investigation can be used as baseline information for the fishery resource management of the region

Versatile binding properties of a di-2-pyridyl ketone nicotinoylhydrazone ligand: Crystal structure of a Cu(II) complex

Six new copper complexes of di-2-pyridyl ketone nicotinoylhydrazone (HDKN) have been synthesized. The complexes have been characterized by a variety of spectroscopic techniques and the structure of [Cu(DKN)2]·H2O has been determined by single crystal X-ray diffraction. The compound [Cu(DKN)2]·H2O crystallized in the monoclinic space group P21 and has a distorted octahedral geometry. The IR spectra revealed the presence of variable modes of chelation for the investigated ligand. The EPR spectra of compounds [Cu2(DKN)2( -N3)2] and [Cu2(DKN)2( -NCS)2] in polycrystalline state suggest a dimeric structure as they exhibited a half field signal, which indicate the presence of a weak interaction between two Cu(II) ions in these complexes

A semi-phenomenological approach to the structure and transport properties of macromolecules in solution

Motiviert durch die Lebenswissenschaften (Life sciences) haben sich Untersuchungen zur Dynamik von Makromolekülen in Lösungen in den vergangenen Jahren zu einem zukunftsweisenden Forschungsgebiet etabliert, dessen Anwendungen von der Biophysik über die physikalische Chemie bis hin zu den Materialwissenschaften reichen. Neben zahlreichen experimentellen Forschungsprogrammen zur räumlichen Struktur und den Transporteigenschaften grosser MolekÄule, wie sie heute praktisch an allen (Synchrotron-) Strahlungsquellen und den Laboren der Biophysik anzutreffen sind, werden gegenwärtig daher auch umfangreiche theoretische Anstrengungen unternommen, um das Diffusionsverhalten von Makromolekülen besser zu erklären. Um neue Wege für eine quantitative Vorhersagen des Translations- und Rotationsverhaltens grosser Moleküle zu erkunden, wurde in dieser Arbeit ein semiphänomenologischer Ansatz verfolgt. Dieser Ansatz erlaubte es, ausgehend von der Hamiltonschen Mechanik des Gesamtsystems 'Molekül + Lösung', eine Mastergleichung für die Phasenraumdichte der Makromoleküle herzuleiten, die den Einfluss der Lösung mittels effektiver Reibungstensoren erfasst. Im Rahmen dieses Ansatzes gelingt es z.B. (i) sowohl den Einfluss der Wechselwirkung zwischen den makromolekularen Gruppen (den sogenannten molekularen beads) und den Lösungsteilchen zu analysieren als auch (ii) die Diffusionseigen schaften für veschiedene thermodynamische Umgebungen zu untersuchen. Ferner gelang es auf der Basis dieser Näherung, die Rotationsbewegung von grossen Molekülen zu beschreiben, die einseitig auf einer Oberfläche festgeheftet sind. Im Vergleich zu den aufwendigen molekulardynamischen (MD) Simulationen grosser Moleküle zeichnet sich die hier dargestellte Methode vor allem durch ihren hohen `Effizienzgewinn' aus, der für komplexe Systeme leicht mehr als fünf Grössenordnungen betragen kann. Dieser Gewinn an Rechenzeit erlaubt bspw. Anwendungen, wie sie mit MD Simulationen wohl auch zukünftig nicht oder nur sehr zögerlich aufgegriffen werden können. Denkbare Anwendungsgebiete dieser Näherung betreffen dabei nicht nur dichte Lösungen, in denen auch die Wechselwirkungen der molekularen beads zu benachbarten Makromolekülen eine Rolle spielt, sondern auch Untersuchungen zu ionischen Flüssigkeiten oder zur Topologie grosser Moleküle.

Influence of the electronic shell structure on the elastic scattering of heavy ions

The interatomic potential of the system I - I at intermediate and small distances is calculated from atomic DFS electron densities within a statistical model. Structures in the potential, due to the electronic shells, are investigated. Calculations of the elastic differential scattering cross section for small angles and several keV impact energies show a detailed peak pattern which can be correlated to individual electronic shell interaction.

Selected configuration interaction with truncation energy error and application to the Ne atom

Selected configuration interaction (SCI) for atomic and molecular electronic structure calculations is reformulated in a general framework encompassing all CI methods. The linked cluster expansion is used as an intermediate device to approximate CI coefficients BK of disconnected configurations (those that can be expressed as products of combinations of singly and doubly excited ones) in terms of CI coefficients of lower-excited configurations where each K is a linear combination of configuration-state-functions (CSFs) over all degenerate elements of K. Disconnected configurations up to sextuply excited ones are selected by Brown's energy formula, ΔEK=(E-HKK)BK2/(1-BK2), with BK determined from coefficients of singly and doubly excited configurations. The truncation energy error from disconnected configurations, Δdis, is approximated by the sum of ΔEKS of all discarded Ks. The remaining (connected) configurations are selected by thresholds based on natural orbital concepts. Given a model CI space M, a usual upper bound ES is computed by CI in a selected space S, and EM=E S+ΔEdis+δE, where δE is a residual error which can be calculated by well-defined sensitivity analyses. An SCI calculation on Ne ground state featuring 1077 orbitals is presented. Convergence to within near spectroscopic accuracy (0.5 cm-1) is achieved in a model space M of 1.4× 109 CSFs (1.1 × 1012 determinants) containing up to quadruply excited CSFs. Accurate energy contributions of quintuples and sextuples in a model space of 6.5 × 1012 CSFs are obtained. The impact of SCI on various orbital methods is discussed. Since ΔEdis can readily be calculated for very large basis sets without the need of a CI calculation, it can be used to estimate the orbital basis incompleteness error. A method for precise and efficient evaluation of ES is taken up in a companion paper

Synthesis, structure and reactivity of novel CuI, CuII and CuIII complexes containing triaza and hexaaza macrocyclic ligands

El treball de tesi s'emmarca dins del camp de la bioinorgànica, disciplina que estudia les propietats estructurals i de reactivitat dels centres actius dels enzims, servint-se de models síntètics de baix pes molecular per tal d'intentar reproduïr la reactivitat presentada per l'enzim i conèixer els mecanismes de reacció a nivell molecular que tenen lloc en els processos biològics.1 Més concretament el treball posa especial èmfasi en els processos d'activació d'oxigen molecular que tenen lloc en les metaloproteïnes de Coure del Tipus 3, com són l'hemocianina i la tirosinasa, ambdues presentant un complex dinuclear de Cu(I)) en el centre actiu de la forma reduïda, capaç d'activar l'O2 cap a espècies de tipus peròxid.2 Un altre camp d'interès ha estat l'estudi dels processos d'activació d'enllaços C-H no activats en hidrocarburs, tant per la seva importàcia a nivell industrial com per comprendre els mecanismes intrínsecs d'aquesta activació a través de metalls de trancisió.3,4 Durant el treball de tesi presentat s'ha desenvolupat la síntesi de nous complexes de Coure(I), Coure(II) y Cu(III) utilitzant lligands macrocíclics de tipus triaza i hexaaza, i s'han estudiat la seves propietats estructurals així com la seva reactivitat. La reacció dels lligands triazacíclics H32m, H2Me33m i H33m amb sals de coure(II) dóna lloc a una reacció de desproporció de Cu(II) per obtenir-se en quantitats equimolars un complex organometàl·lic de Cu(III) i un complex de Cu(I). La caracterizació estructural exhaustiva dels complexes del tipus aryl-Cu(III) evidencia la formació d'un enllaç organometàl·lic entre l'àtom de Cu(III) i el carboni més próxim de l'anell aromàtic del lligand. Aquesta reacció, a més de representar una nova forma de desproporció en la química del Cu, suposa l'activació d'un enllaç C-H aromàtic a temperatura ambient que, mitjançant l'estudi cinètic d'aquesta desproporció per espectroscòpia UV-Vis, dels càlcul de l'efecte cinètic isotòpic utilitzant el lligand deuterat en el C-H de l'anell, juntament amb el recolzament teòrics dels càlculs DFT per a la optimització de geometries d'intermedis de reacció, ens permeten proposar un mecanisme de reacció pel nostre sistema, on l'activació de l'enllaç C-H aromàtic transcorre per la formació d'un enllaç de tipus agòstic C-H ? Cu(II),5 seguit de la desprotonació del C-H aromàtic per acció d'una base i posterior transferència electrònica per obtenir el complex organometàlic de Cu(III) i el complex de de Cu(I). En quant a la reactivitat d'aquests complexes organometàl·lics aryl-Cu(III) s'ha observat que una base en medi aquós causa la inestabilitat d'aquests compostos, evolucionant cap a la inserció d'un àtom d'oxigen sobre la posició activada de l'anell aromàtic, per a donar lloc a un complex dinuclear de Cu(II) amb dos grups fenoxo actuant de pont entre els àtoms metàl·lics. La reacció transcorre per un intermedi colorejat, caracteritzat com el complex ayl-Cu(III) monodesprotonat en una de les seves amines benzíliques, els quals s'observen igualment en la reacció dels correponents complexos de Cu(I) amb oxigen molecular (O2). És en els nostres sistemes en els quals es descriu per primera vegada la participació d'intermedis organometàl·lics Cu(III)-C en processos d'hidroxilació aromàtica, tals com el desenvolupat per l'enzim tirosinasa o per alguns dels seus models químics de síntesi.6,7,8 S'han estudiat les propietats magnètiques dels quatre bis(fenoxo)complexes de Cu(II) descrits, obtenint-se uns acoplaments de tipus antiferromagnètic o ferromagnètic de diversa magnitud, depenent del solapament orbitalari a l'enllaç Cu-O, a través del qual es produeix el superintercanvi. Nous complexos de Cu(I) sintetitzats amb lligands hexaazamacrocíclics han estat estudiats, i posant especial èmfasi a la seva reactivitat respecta a l'activació d'oxigen molecular (O2). S'ha observat una reactivitat diferenciada segons la concentració de complex de Cu(I) utilitzada, de manera que a altes concentracions s'obté un carbonato complex tetranuclear de Cu(II) per fixació de CO2 atmosfèric, mentre que a baixes concentracions s'observa la hidroxilació aromàtica intramolecular d'un dels anells benzílics del lligand, reacció que presumiblement transcorre per atac electrofílic d'un peroxo complex intermedi sobre el sistema ? de l'anell.6 Els resultats obtinguts en aquest treball ens mostren la facilitat per activar enllaços C-H aromàtics per metalls de transició de la primera sèrie (Cu, Ni) quan aquests estan suficientment pròxims a l'enllaç C-H, en unes condicions de reacció molt suaus (1atm., temperatura ambient). Els nous complexos organometàl·lics Aryl-Cu(III) són el producte d'una nova reacció de desproporció de Cu(II), així com un posició aromàtica activada que podria ser el punt de partida per l'estudi de funcionalització selectiva d'aquests grups aromàtics.

Electronic structure of point defects in controlled self-doping of the TiO2 (110) surface: Combined photoemission spectroscopy and density functional theory study

Point defects in metal oxides such as TiO2 are key to their applications in numerous technologies. The investigation of thermally induced nonstoichiometry in TiO2 is complicated by the difficulties in preparing and determining a desired degree of nonstoichiometry. We study controlled self-doping of TiO2 by adsorption of 1/8 and 1/16 monolayer Ti at the (110) surface using a combination of experimental and computational approaches to unravel the details of the adsorption process and the oxidation state of Ti. Upon adsorption of Ti, x-ray and ultraviolet photoemission spectroscopy (XPS and UPS) show formation of reduced Ti. Comparison of pure density functional theory (DFT) with experiment shows that pure DFT provides an inconsistent description of the electronic structure. To surmount this difficulty, we apply DFT corrected for on-site Coulomb interaction (DFT+U) to describe reduced Ti ions. The optimal value of U is 3 eV, determined from comparison of the computed Ti 3d electronic density of states with the UPS data. DFT+U and UPS show the appearance of a Ti 3d adsorbate-induced state at 1.3 eV above the valence band and 1.0 eV below the conduction band. The computations show that the adsorbed Ti atom is oxidized to Ti2+ and a fivefold coordinated surface Ti atom is reduced to Ti3+, while the remaining electron is distributed among other surface Ti atoms. The UPS data are best fitted with reduced Ti2+ and Ti3+ ions. These results demonstrate that the complexity of doped metal oxides is best understood with a combination of experiment and appropriate computations.

On the evolution of the solar wind between 1 and 5 AU at the time of the Cassini Jupiter flyby: Multispacecraft observations of interplanetary coronal mass ejections including the formation of a merged interaction region

The Cassini flyby of Jupiter occurred at a time near solar maximum. Consequently, the pre-Jupiter data set reveals clear and numerous transient perturbations to the Parker Spiral solar wind structure. Limited plasma data are available at Cassini for this period due to pointing restrictions imposed on the instrument. This renders the identification of the nature of such structures ambiguous, as determinations based on the magnetic field data alone are unreliable. However, a fortuitous alignment of the planets during this encounter allowed us to trace these structures back to those observed previously by the Wind spacecraft near the Earth. Of the phenomena that we are satisfactorily able to trace back to their manifestation at 1 AU, two are identified as being due to interplanetary coronal mass ejections. One event at Cassini is shown to be a merged interaction region, which is formed from the compression of a magnetic cloud by two anomalously fast solar wind streams. The flux-rope structure associated with this magnetic cloud is not as apparent at Cassini and has most likely been compressed and deformed. Confirmation of the validity of the ballistic projections used here is provided by results obtained from a one-dimensional magnetohydrodynamic projection of solar wind parameters measured upstream near the Earth. It is found that when the Earth and Cassini are within a few tens of degrees in heliospheric longitude, the results of this one-dimensional model predict the actual conditions measured at 5 AU to an impressive degree. Finally, the validity of the use of such one-dimensional projections in obtaining quasi-solar wind parameters at the outer planets is discussed.

Interfacial structure of wild-type and mutant forms of puroindoline-b bound to DPPG monolayers

The interaction of wild-type puroindoline-b (Pin-b+) and two mutant forms having single residue substitutions (G46S or W44R) with L-alpha-dipalmitoylphosphatidyl-dl-glycerol (DPPG) as a Langmuir monolayer at the air/water interface was investigated by neutron reflectivity (NR) and Brewster angle microscopy (BAM). NR profiles were fitted using a three-layer model to enable differences in penetration of protein between the lipid headgroup and acyl regions to be determined. The data showed similar surface excesses for each of the three proteins at the interface; however, it was revealed that the depth of penetration of protein into the lipid region differed for each protein with Pin-b+ penetrating further into the acyl region of the lipid compared to the mutant forms of the protein that interacted with the headgroup region only. BAM images revealed that the domain structure of the DPPG monolayers was disrupted when Pin-b+ adsorption had reached equilibrium, suggesting protein penetration had led to compression of the lipid region. In contrast, the domain structure was unaffected by the W44R mutant, suggesting no change in compression of the lipid region and hence little or no penetration of protein into the lipid layer.

C–H local modes in cyclobutene. II. Laser photoacoustic studies 10 000–17 000 cm−1. Vibrational structure and C–H local mode dynamics

In part I of this study [Baggott, Clase, and Mills, Spectrochim. Acta Part A 42, 319 (1986)] we presented FTIR spectra of gas phase cyclobutene and modeled the v=1–3 stretching states of both olefinic and methylenic C–H bonds in terms of a local mode model. In this paper we present some improvements to our original model and make use of recently derived ‘‘x,K relations’’ to find the equivalent normal mode descriptions. The use of both the local mode and normal mode approaches to modeling the vibrational structure is described in some detail. We present evidence for Fermi resonance interactions between the methylenic C–H stretch overtones and ring C–C stretch vibrations, revealed in laser photoacoustic spectra in the v=4–6 region. An approximate model vibrational Hamiltonian is proposed to explain the observed structure and is used to calculate the dynamics of the C–H stretch local mode decay resulting from interaction with lower frequency ring modes. The implications of our experimental and theoretical studies for mode‐selective photochemistry are discussed briefly.

Molecule modeling of human pentameric alpha(7) neuronal nicotinic acetylcholine receptor and its interaction with its agonist and competitive antagonist

The nicotinic Acetylcholine Receptor (nAChR) is the major class of neurotransmitter receptors that is involved in many neurodegenerative conditions such as schizophrenia, Alzheimer's and Parkinson's diseases. The N-terminal region or Ligand Binding Domain (LBD) of nAChR is located at pre- and post-synaptic nervous system, which mediates synaptic transmission. nAChR acts as the drug target for agonist and competitive antagonist molecules that modulate signal transmission at the nerve terminals. Based on Acetylcholine Binding Protein (AChBP) from Lymnea stagnalis as the structural template, the homology modeling approach was carried out to build three dimensional model of the N-terminal region of human alpha(7)nAChR. This theoretical model is an assembly of five alpha(7) subunits with 5 fold axis symmetry, constituting a channel, with the binding picket present at the interface region of the subunits. alpha-netlrotoxin is a potent nAChR competitive antagonist that readily blocks the channel resulting in paralysis. The molecular interaction of alpha-Bungarotoxin, a long chain alpha-neurotoxin from (Bungarus multicinctus) and human alpha(7)nAChR seas studied. Agonists such as acetylcholine, nicotine, which are used in it diverse array of biological activities, such as enhancements of cognitive performances, were also docked with the theoretical model of human alpha(7)nAChR. These docked complexes were analyzed further for identifying the crucial residues involved in interaction. These results provide the details of interaction of agonists and competitive antagonists with three dimensional model of the N-terminal region of human alpha(7)nAChR and thereby point to the design of novel lead compounds.