Nonlocal effects in the 8Be breakup

A collective Hamiltonian for a two alpha particles aggregate, which describes the 8Be nucleus, encompassing a collective potential and an inertia function of that system, is obtained and analyzed through the use of a technique - derived from an approach of the generator coordinate method (GCM) - which allows for the extraction of collective information. The nucleon-nucleon interaction considered here is the one proposed by Volkov plus the Coulomb repulsion. It is shown that nonlocal effects appear in those collective functions describing the spontaneously occurring breakup process. Furthermore, the result for the inertia function stands for a microscopically generated evidence supporting a double-folding-based model of the real part of the nucleus-nucleus nonlocal interaction recently proposed.

Hydrogen bond and the resonance effect on the formamide-water complexes

The interaction of formamide and the two transition states of its amide group rotation with one, two, or three water molecules was studied in vacuum. Great differences between the electronic structure of formamide in its most stable form and the electronic structure of the transition states were noticed. Intermolecular interactions were intense, especially in the cases where the solvent interacted with the amide and the carbonyl groups simultaneously. In the transition states, the interaction between the lone pair of nitrogen and the water molecule becomes important. With the aid of the natural bond orbitals, natural resonance theory, and electron localization function (ELF) analyses an increase in the resonance of planar formamide with the addition of successive water molecules was observed. Such observation suggests that the hydrogen bonds in the formamidewater complexes may have some covalent character. These results are also supported by the quantitative ELF analyses. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012

Self-Assembly of Poly(4-vynil-N-alkylpyridinium) Bromide onto Silica: Effect of Side-Chain Length on Structural Aspects at a Molecular Level

Self-assembly of poly(4-vynil-N-alkyl)pyridinium bromide with alkyl side chains of 2, 5, 7, 10, or 16 carbons from ethanolic solutions onto flat silica surfaces was studied by means of ellipsometry, atomic force microscopy (AFM), contact angle measurements, and sum-frequency generation (SFG) vibrational spectroscopy in the CH3 and CH2 stretch region. Ab initio quantum-chemical calculations on the N-alkylpyridinium side-group with restricted Hartree-Fock (RHF) method and 6-311G (d,p) basis set were C one to estimate the charge distribution along the pyridinium ring and the alkyl side-chain. SFG results showed that longer side chains promote the disorientation of the alkyl groups at the surface, corroborating with the contact angle values. AFM images revealed film homogeneity, regardless the alkyl side group. However, after 24 h contact with water, ringlike structures appeared on the film surfaces, when the polycation alkyl side chain had 7 or less carbons, and as the alkyl chain increased to 10 or 16 carbons, the films dewetted because the hydrophobic interactions prevailed over the electrostatic interactions between the pyridinium charged groups and the negatively charged SiO2 surface. Under acid conditions (HCl 0.1 mol.L-1), the film mean thickness values decreased up to 50% of original values when the alkyl side chains were ethyl or pentyl groups due to ion-pair disruption, but for longer groups they remained unchanged. Quantum-chemical optimization and Mulliken electron population showed that (i) from C2 to C15 the positive charge at the headgroup (HG) decreased 0.025, while the charge at combined HG + alpha-CH2 increased 0.037; and (ii) for C6 or longer, the alkyl side group presents a tilt in the geometry, moving away from the plane. Such effects summed up over the whole polymer chain give support to suggest that when the side chains are longer than 7 carbons, the hydrophobic interaction decreases film stability and increases acid resistance.

Theoretical and experimental studies on the electronic, optical, and structural properties of poly-pyrrole-2-carboxylic acid films

A theoretical approach is used here to explain experimental results obtained from the electrosynthesis of polypyrrole-2-carboxylic acid (PPY-2-COOH) films in nonaqueous medium. An analysis of the Fukui function (reactivity index) indicates that the monomer (pyrrole-2-carboxylic acid, PY-2-COOH), and dimers and trimers are oxidized in the C4 or C5 positions of the heterocyclic ring of the PY-2-COOH structure. After calculating the heat of formation using semiempirical Austin Model 1 post-Hartree-Fock parameterization for dimer species, both C4 and C5 positions adjacent to the aromatic rings of PPY-2-COOH were considered the most susceptible ones to oxidative coupling reactions. The ZINDO-S/CI semiempirical method was used to simulate the electronic transitions typically seen in the UV-VIS-NIR range in monomer and oligomers with different conjugation lengths. The use of an electrochemical quartz crystal microbalance provides sufficient information to propose a polymerization mechanism of PY-2-COOH based on molecular modeling and experimental results.

Coupled-Cluster-Berechnungen von Parametern der Kernspin-Resonanz-Spektroskopie

Coupled-Cluster-Berechnungen von Parametern derKernspin-Resonanz-Spektroskopie Dissertationsschrift von Alexander A.Auer, Mainz 2002 Im Rahmen einer Studie der Berechnung von 13C-Verschiebungenwerdendie Einfluesse von Elektronenkorrelation, Basissatz,Gleichgewichtsgeometrie sowie Schwingungs- und Rotationseffekten separat betrachtet.Dabei zeigt sich, dass dieCoupled-Cluster-Singles-Doubles-Methode mitstoerungstheoretischer Behandlung der Dreifachanregungen(CCSD(T)) mit entsprechend grossen Basissaetzen bei Beruecksichtigung derNullpunktsschwingungseffekte Ergebnisse mit ca. 1 ppm Abweichung zum Experiment liefert. Eine Analyse der Elektronenkorrelationseffekte beiCoupled-Cluster- (CC-) Berechnungen von indirekten Spin-Spin-Kopplungskonstanten zeigt, dassCC-Methoden mit Hartree-Fock-Orbitalrelaxation zur Berechnung derKopplungskonstanten ungeeignet sind. Eine Loesung ist die Verwendung unrelaxierter CC-Methoden,in denendie HF-Orbitalrelaxation aus der Berechnung der gestoertenWellenfunktion ausgeschlossen wird. Full-Configuration-Interaction-Berechnungen fuer Borhydridzeigen,dass auf CC-Singles-Doubles-Niveau (CCSD) 94% und aufCC-Singles-Doubles-Triples-Niveau (CCSDT) 99% der Korrelationseffekte beschrieben werden. Weiterhin istdie Beruecksichtigung der Nullpunktsschwingung sowie die Wahl eines ausreichend grossen Basissatzes wichtig. Auf Grundlage der vorangegangenen Studien werden im letztenTeil zwei Beispiele zur Anwendung hochgenauer Berechnungen vonNMR-Parametern vorgestellt.Im Rahmen einer Studie der Spin-Spin-Kopplungskonstanten vonCyclopentan wird eine Karplus-Beziehungzwischen den Kopplungskonstanten und der Konformation desMolekuels aufgestellt, desweiteren werden die NMR-Parameter von Methylidinphosphanuntersucht.

First principle study of ions in water and ionic liquids

Die beiden in dieser Arbeit betrachteten Systeme, wässrige Lösungen von Ionen und ionische Flüssigkeiten, zeigen vielfältige Eigenschaften und Anwendungsmöglichkeiten, im Gegensatz zu anderen Systemen. Man findet sie beinahe überall im normalen Leben (Wasser), oder ihre Bedeutung wächst (ioinische Flüssigkeiten). Der elektronische Anteil und der atomare Anteil wurden getrennt voneinander untersucht und im Zusammenhang analysiert. Mittels dieser Methode konnten die in dem jeweiligen System auftretenden Mechanismen genauer untersucht werden. Diese Methode wird "Multiscale Modeling" genannt, dabei werden die Untereinheiten eines Systems genauer betrachtet, wie in diesem Fall die elektronischen and atomaren Teilsystem. Die Ergebnisse, die aus den jeweiligen Betrachtungen hervorgehen, zeigen, dass, im Falle von hydratisierten Ionen die Wasser-Wasser Wechselwirkungen wesentlich stärker sind als die elektrostatischen Wechselwirkung zwischen Wasser und dem Ion. Anhand der Ergebnisse ergibt sich, dass normale nicht-polarisierbare Modelle ausreichen, um Ionen-Wasser Lösungen zu beschreiben. Im Falle der ionischen Flüssigkeiten betrachten wir die elektronische Ebene mittels sehr genauer post-Hartree-Fock Methoden und DFT, deren Ergebnisse dann mit denen auf molekularer Ebene (mithilfe von CPMD/klassischer MD) in Beziehung gesetzt werden. Die bisherigen Ergebnisse zeigen, dass die Wasserstoff-Brückenbindungen im Fall der ionischen Flüssigkeiten nicht vernachässigt werden können. Weiterhin hat diese Studie herausgefunden, dass die klassischen Kraftfelder die Elektrostatik (Dipol- und Quadrupolmomente) nicht genau genug beschreibt. Die Kombination des mikroskopischen Mechanismus und der molekularen Eigenschaften ist besonders sinnvoll um verschiedene Anhaltspunkte von Simualtionen (z.B. mit klassische Molekular-Dynamik) oder Experimenten zu liefern oder solche zu erklären.

Theoretical study of correlated systems using hybrid functionals

Diese Arbeit unterstreicht das Potential von Hybridfunktionalen (B3LYP) für die Untersuchung einer großen Bandbreite von Systemen. Durch die Einbeziehung der exakten Hartree-Fock Austauschenergie kann B3LYP für molekulare und kristalline Systeme eingesetzt werden. Zum Beispiel können stark korrelierte Systeme mit B3LYP erfolgreich erforscht werden. Die elektronische Struktur von PAHs wurde mit B3LYP Hybriddichtefunktionalen untersucht. Mit der ∆SCF-Methode wurden Elektronenbindungsenergien bestimmt, welche die mit UPS gewonnenen experimentellen Resultate bestätigen und ergänzen. Symmetrieeigenschaften der molekularen Orbitale wurden analysiert, um eine Zuordnung und Einschätzung der zugehörigen Signalstärke zu ermöglichen. Während σ-artige Orbitale nur schwer durch UPS-Messungen an dünnen Filmen detektiert werden können, bieten Rechnungen eine detaillierte Einsicht in die verborgenen Teile der Spektren.rnWeiterhin wurden π−π-Komplexe untersucht, welche von verschiedenen Donor- und Akzeptor-Molekülen gebildet werden. Die Moleküle basieren auf polyzyklischen, aromatischen Kohlenwasserstoffen. Für Ladungstransferkomplexe finden DFT Rechnungen ein Minimum in der Oberfläche der potentiellen Energie. Diese attraktive Wechselwirkung wird durch Coulombanziehung verursacht. Allerdings ist die Coulombanziehung nicht die stärkste Wechselwirkung in Ladungstransferkomplexen. Die Einbeziehung von van der Waals-Korrekturen verbessert den intermolekularen Abstand und die Bindungsenergie.rnEine Verkleinerung der intermolekularen Abstände führt zu einer großen Verschiebung der HOMO- und LUMO-Energie.rnAus der Klasse der kristallinen korrelierten Systeme wurden Rb4O6 und FeSe untersucht. Im Falle von Rb4O6 führen Ladungsordnung und Korrelationen zu einem isolierenden Grundzustand. Das hypothetische druckabhängige Phasendiagramm wurde untersucht. Eine Erhöhung des Drucks führt zu einer vergrößerten Bandlücke. Bei etwa 75 GPa wird die Bandbreite W größer als der Bandabstand U und das System nimmt einen homogen gemischt valenten Zustand mit teilweise besetzten π−π-Orbitalen an. Für Drücke ab 160 GPa wird W sehr viel größer als U und das System wird metallisch.rnIm Fall von FeSe finden wir eine korrelierte und isolierende Phase bei hohen Drücken, während das System bei niedrigen Drücken supraleitendes Verhalten zeigt. Die Berechnungen der Elektronenstruktur mit dem Hybridfunktional B3LYP führt zum korrekten halbleitenden Grundzustand in der NiAs- und MnP-Struktur von FeSe. Die Rolle der Korrelationen, der Stöchiometrie und der Nähe zum Magnetismus wird besprochen. Im Speziellen wird gezeigt, dass die Phase mit NiAs-Struktur starke lokale Korrelationen aufweist, was zu einem halbleitenden Zustand in einem weiten Druckbereich führt.

The S-1/S-2 exciton interaction in 2-pyridone center dot 6-methyl-2-pyridone: Davydov splitting, vibronic coupling, and vibronic quenching

The excitonic splitting between the S-1 and S-2 electronic states of the doubly hydrogen-bonded dimer 2-pyridone center dot 6-methyl-2-pyridone (2PY center dot 6M2PY) is studied in a supersonic jet, applying two-color resonant two-photon ionization (2C-R2PI), UV-UV depletion, and dispersed fluorescence spectroscopies. In contrast to the C-2h symmetric (2-pyridone) 2 homodimer, in which the S-1 <- S-0 transition is symmetry-forbidden but the S-2 <- S-0 transition is allowed, the symmetry-breaking by the additional methyl group in 2PY center dot 6M2PY leads to the appearance of both the S-1 and S-2 origins, which are separated by Delta(exp) = 154 cm(-1). When combined with the separation of the S-1 <- S-0 excitations of 6M2PY and 2PY, which is delta = 102 cm(-1), one obtains an S-1/S-2 exciton coupling matrix element of V-AB, el = 57 cm(-1) in a Frenkel-Davydov exciton model. The vibronic couplings in the S-1/S-2 <- S-0 spectrum of 2PY center dot 6M2PY are treated by the Fulton-Gouterman single-mode model. We consider independent couplings to the intramolecular 6a' vibration and to the intermolecular sigma' stretch, and obtain a semi-quantitative fit to the observed spectrum. The dimensionless excitonic couplings are C(6a') = 0.15 and C(sigma') = 0.05, which places this dimer in the weak-coupling limit. However, the S-1/S-2 state exciton splittings Delta(calc) calculated by the configuration interaction singles method (CIS), time-dependent Hartree-Fock (TD-HF), and approximate second-order coupled-cluster method (CC2) are between 1100 and 1450 cm(-1), or seven to nine times larger than observed. These huge errors result from the neglect of the coupling to the optically active intra-and intermolecular vibrations of the dimer, which lead to vibronic quenching of the purely electronic excitonic splitting. For 2PY center dot 6M2PY the electronic splitting is quenched by a factor of similar to 30 (i.e., the vibronic quenching factor is Gamma(exp) = 0.035), which brings the calculated splittings into close agreement with the experimentally observed value. The 2C-R2PI and fluorescence spectra of the tautomeric species 2-hydroxypyridine center dot 6-methyl-2-pyridone (2HP center dot 6M2PY) are also observed and assigned. (C) 2011 American Institute of Physics.

Spin-strain coupling in a 3-D transition metal oxides

ab-initio Hartree Fock (HF), density functional theory (DFT) and hybrid potentials were employed to compute the optimized lattice parameters and elastic properties of perovskite 3-d transition metal oxides. The optimized lattice parameters and elastic properties are interdependent in these materials. An interaction is observed between the electronic charge, spin and lattice degrees of freedom in 3-d transition metal oxides. The coupling between the electronic charge, spin and lattice structures originates due to localization of d-atomic orbitals. The coupling between the electronic charge, spin and crystalline lattice also contributes in the ferroelectric and ferromagnetic properties in perovskites. The cubic and tetragonal crystalline structures of perovskite transition metal oxides of ABO3 are studied. The electronic structure and the physics of 3-d perovskite materials is complex and less well considered. Moreover, the novelty of the electronic structure and properties of these perovskites transition metal oxides exceeds the challenge offered by their complex crystalline structures. To achieve the objective of understanding the structure and property relationship of these materials the first-principle computational method is employed. CRYSTAL09 code is employed for computing crystalline structure, elastic, ferromagnetic and other electronic properties. Second-order elastic constants (SOEC) and bulk moduli (B) are computed in an automated process by employing ELASTCON (elastic constants) and EOS (equation of state) programs in CRYSTAL09 code. ELASTCON, EOS and other computational algorithms are utilized to determine the elastic properties of tetragonal BaTiO3, rutile TiO2, cubic and tetragonal BaFeO3 and the ferromagentic properties of 3-d transition metal oxides. Multiple methods are employed to crosscheck the consistency of our computational results. Computational results have motivated us to explore the ferromagnetic properties of 3-d transition metal oxides. Billyscript and CRYSTAL09 code are employed to compute the optimized geometry of the cubic and tetragonal crystalline structure of transition metal oxides of Sc to Cu. Cubic crystalline structure is initially chosen to determine the effect of lattice strains on ferromagnetism due to the spin angular momentum of an electron. The 3-d transition metals and their oxides are challenging as the basis functions and potentials are not fully developed to address the complex physics of the transition metals. Moreover, perovskite crystalline structures are extremely challenging with respect to the quality of computations as the latter requires the well established methods. Ferroelectric and ferromagnetic properties of bulk, surfaces and interfaces are explored by employing CRYSTAL09 code. In our computations done on cubic TMOs of Sc-Fe it is observed that there is a coupling between the crystalline structure and FM/AFM spin polarization. Strained crystalline structures of 3-d transition metal oxides are subjected to changes in the electromagnetic and electronic properties. The electronic structure and properties of bulk, composites, surfaces of 3-d transition metal oxides are computed successfully.

Single crystal raman spectroscopy of natural paulmooreite Pb2As2O5 and in comparison with the synthesised analogue

The single crystal Raman spectra of natural mineral paulmooreite Pb2As2O5 from the Långban locality, Filipstad district, Värmland province, Sweden are presented for the first time. It is a monoclinic mineral containing an isolated [As2O5]4-. Depolarised and single crystal spectra of the natural and synthetic sample compare favorably and are characterized by strong bands around 186 and 140 cm-1 and three medium bands at 800 – 700 cm-1. Band assignments were made based on band symmetry and spectral comparison between experimental band positions and those resulting from Hartree-Fock calculation of an isolated [As2O5]4- ion. Spectral comparison was also made with lead arsenites such as synthetic PbAs2O4 and Pb2(AsO2)3Cl and natural finnemanite in order to determine the contribution of the terminal and bridging O in paulmooreite. Bands at 760 – 733 cm-1 were assigned to terminal As-O vibrations, whereas stretches of the bridging O occur at 562 and 503 cm-1. The single crystal spectra showed good mode separation, allowing bands to be assigned a symmetry species of Ag or Bg.

A theoretical study of C4B isomers. The interconversion of CCBCC and CCCCB via cyclic C4B

Theory suggests that CCBCC (1) will rearrange to planar cyclo-C4B (19) if the excess energy of 1 is greater than or equal to16.1 kcal mol(-1) [calculations at the CCSD(T)/aug-cc-pVTZ//B3LYP/6-31G(d) level of theory]. Cyclo-C4B lies only 1.1 kcal mol(-1) above CCBCC. The planar nature of symmetrical cyclo-C4B is attributed to multicentered bonding involving boron. If cyclo-C4B (19) has an excess energy of greater than or equal to24.4 kcal mol-1, it may ring open to form CCCCB (3).

Anomeric effect in sulfur-containing systems: An Ab-initio study

The anomeric effect in S---C---S and O---C---S systems was studied by using closed-shell Hartree-Fock theory. A comparison of the STO-3G level with the 4–31G and 6–31G* levels was performed for the O---C---O system, and the STO-3G level found adequate for study of the anomeric effect. Optimization of bond lengths and angles was conducted at the STO-3G level and limited studies were made at the 4–31G level. The nature of the torsional potential curves is compared for the O---C---O, O---C---S, and S---C---S systems. The possible reasons for the decreased anomeric effect in sulfur systems are discussed.

Vibrational force constant and electron relaxation in H2 and Li2

The force constants of H2 and Li2 are evaluated employing their extended Hartree-Fock wavefunctions by a polynomial fit of their force curves. It is suggested that, based on incomplete multiconfiguration Hartree-Fock wavefunctions, force constants calculated from the energy derivatives are numerically more accurate than those obtained from the derivatives of the Hellmann-Feynman forces. It is observed that electrons relax during the nuclear vibrations in such a fashion as to facilitate the nuclear motions.

Calculation of Coulomb interaction strengths for 3d transition metals and actinides

Coulomb interaction strengths (Udd and Uff) have been calculated from Hartree-Fock-Slater atomic calculations for 3d transition and 5f actinide elements, respectively. By decomposing the different contributions to the response (screening) to the 3d charge fluctuation, we show that a substantial reduction in Udd arises due to the relaxation of the 3d charge distribution itself. This, combined with the screening due to the response of the 4s charge density, is shown to provide a very compact screening charge comparable to the metallic case, explaining the success of the atomic calculations for estimating U even in the metals. A pronounced dependence of Udd (or Uff) on the number of electrons nd (nf) or the electronic configuration is also shown here.

Is a CImage C quadruple bond possible?

Ab initio computations Predict a minimum for a carbon-carbon quadruple bond in C2. While the computed C-C separation, 1.128 angstrom, fits Pauling's bond order-bond length relationship well, this result is an artifact of the restricted Hartree Fock theory.