A theoretical study of the A(2)Sigma(+)-X-2 Pi system of the SiP molecule

The A (2)Sigma(+) and X(2)Pi electronic states of the SiP species have been investigated theoretically at a very high level of correlation treatment (CASSCF/MRSDCI). Very accurate potential energy curves are presented for both states, as well as the associated spectroscopic constants as derived from the vib-rotational energy levels determined by means of the numerical solution of the radial Schrodinger equation. Electronic transition moment function, oscillator strengths, Einstein coefficients for spontaneous emission, and Franck-Condon factors for the A(2)Sigma(+)-X(2)Pi system have been calculated. Dipole moment functions and radiative lifetimes for both states have also been determined. Spin-orbit coupling constants are also reported. The radiative lifetimes for the A(2)Sigma(+) state, taking into account the spin-orbit diagonal correction to the X(2)Pi state, decrease from a value of 138 ms at v' = 0 to 0.48 ms at v' = 8, and, for the X(2)Pi state, from 2.32 s at v = 1 to 0.59 s at v = 5. Vibrational and rotational transitions are expected to be relatively strong.

The sensitization of the ligand-field state of the hexaammineruthenium(II) complex ion by organic compounds

The sensitized photolysis of [Ru(NH3)(6)](2+) by the organic dye rhodamine B and biacetyl was studied under conditions in which only the sensitizer absorbs. The reaction products resulting from ammonia aquation and Ru(II) to Ru(III) oxidation are the same for direct and sensitized photolysis. The energy transfer rate constant, calculated from the fluorescence quenching of rhodamine B, is similar to that estimated from the limiting quantum yield of the photosensitized photoaquation of the complex. Both reactions originate from a common reactive low-lying ligand-field (LF) state, which is also responsible for the direct photolysis reactions. This state, which leads directly to photoaquation, seems to have a certain charge transfer to solvent (CTTS) character, which is responsible for the photo-oxidation products. Sensitization is effective with rhodamine B (17 450 cm(-1)) and biacetyl (19 000 cm(-1)), whereas no reaction is observed with neutral red (16 900 cm(-1)). These results show that the excited state responsible for the photochemical reactions lies in the energy range between 16 900 cm(-1) and 17 700 cm(-1) and possesses spin-orbit character.

ESR STUDY OF CUCL2 ADSORBED ON A CHEMICALLY-MODIFIED SILICA-GEL SURFACE WITH BENZIMIDAZOLE MOLECULE

The ESR spectrum of CuCl2 adsorbed onto a silica gel surface chemically modified with the benzimidazole molecule showed that the surface complex has an octahedral symmetry with tetragonal distortion. The measured ESR parameters were g(parallel to) = 2.287, g(perpendicular to) = 2.062, A(parallel to) = 153 G and superhyperfine splitting A(N) = 15 G. The fit of the theoretical expressions to the experimental data was very reasonable. The effective spin orbit coupling constant for Cu2+ was reduced from its normal free ion value of lambda = -828 cm(-1) by as much as 30%. This reduction of lambda is normal in the solid state and in frozen solution complexes.

Magnetic-field and confinement effects on the effective Land, g factor in AlxGa1-xAs parabolic quantum wells

The magnetic-field and confinement effects on the Land, factor in AlxGa1-xAs parabolic quantum wells under magnetic fields applied parallel or perpendicular to the growth direction are theoretically studied. Calculations are performed in the limit of low temperatures and low electron density in the heterostructure. The g factor is obtained by taking into account the effects of non-parabolicity and anisotropy of the conduction band through the 2 x 2 Ogg-McCombe Hamiltonian, and by including the cubic Dresselhaus spin-orbit term. A simple formula describing the magnetic-field dependence of the effective Land, factor is analytically derived by using the Rayleigh-Schrodinger perturbation theory, and it is found in good agreement with previous experimental studies devoted to understand the behavior of the g factor, as a function of an applied magnetic field, in semiconductor heterostructures. Present numerical results for the effective Land, factor are shown as functions of the quantum-well parameters and magnetic-field strength, and compared with available experimental measurements.

Anisotropy of the effective Lande factor in AlxGa1-x As parabolic quantum wells under applied magnetic fields

The anisotropy of the effective Lande factor in Al(x)Gal(1-x)As parabolic quantum wells under magnetic fields is theoretically investigated. The non-parabolicity and anisotropy of the conduction band are taken into account through the Ogg-McCombe Hamiltonian together with the cubic Dresselhaus spin-orbit term. The calculated effective g factor is larger when the magnetic field is applied along the growth direction. As the well widens, its anisotropy increases sharply and then decreases slowly. For the considered field strengths, the anisotropy is maximum for a well width similar to 50 angstrom. Moreover, this anisotropy increases with the field strength and the maximum value of the aluminum concentration within the quantum well. (C) 2010 Elsevier B.V. All rights reserved.

Fock terms in the quark-meson coupling model

The mean field description of nuclear matter in the quark-meson coupling model is improved by the inclusion of exchange contributions (Fock terms). The inclusion of Fock terms allows us to explore the momentum dependence of meson-nucleon vertices and the role of pionic degrees of freedom in matter. It is found that the Fock terms maintain the previous predictions of the model for the in-medium properties of the nucleon and for the nuclear incompressibility. The Fock terms significantly increase the absolute values of the single-particle, four-component scalar and vector potentials, a feature that is relevant for the spin-orbit splitting in finite nuclei. © 1999 Elsevier Science B.V.

A theoretical study of the A2 ∑+-X2∏ system of the SiP molecule

The A2∑+ and Z2∏ electronic states of the SiP species have been investigated theoretically at a very high level of correlation treatment (CASSCF/MRSDCI). Very accurate potential energy curves are presented for both states, as well as the associated spectroscopic constants as derived from the vib-rotational energy levels determined by means of the numerical solution of the radial Schrödinger equation. Electronic transition moment function, oscillator strengths, Einstein coefficients for spontaneous emission, and Franck-Condon factors for the A2∑+-X2∏ system have been calculated. Dipole moment functions and radiative lifetimes for both states have also been determined. Spin-orbit coupling constants are also reported. The radiative lifetimes for the A2∑+ state, taking into account the spin-orbit diagonal correction to the X2∏ state, decrease from a value of 138 ms at v′ = 0 to 0.48 ms at v′ = 8, and, for the X2∏ state, from 2.32 s at v″ = 1 to 0.59 s at v″ = 5. Vibrational and rotational transitions are expected to be relatively strong.

Dynamics of rotation of super-Earths

We numerically investigate the dynamics of rotation of several close-in terrestrial exoplanet candidates. In our model, the rotation of the planet is disturbed by the torque of the central star due to the asymmetric equilibrium figure of the planet. We model the shape of the planet by a Jeans spheroid. We use surfaces of section and spectral analysis to explore numerically the rotation phase space of the systems adopting different sets of parameters and initial conditions close to the main spin-orbit resonant states. One of the parameters, the orbital eccentricity, is critically discussed here within the domain of validity of orbital circularization timescales given by tidal models. We show that, depending on some parameters of the system like the radius and mass of the planet, eccentricity etc., the rotation can be strongly perturbed and a chaotic layer around the synchronous state may occupy a significant region of the phase space. 55 Cnc e is an example. © 2013 Springer Science+Business Media Dordrecht.

Dinâmica de rotação de exoplanetas tipo terrestre com perturbação de terceiro corpo

In this work we study some topics of Celestial Mechanics, namely the problem of rigid body rotation and “spin-orbit” resonances. Emphasis is placed on the problem formulation and applications to some exoplanets with physical parameters (e.g. mass and radius) compatible with a terrestrial type constitution (e.g. rock) belonging to multiple planetary systems. The approach is both analytical and numerical. The analytical part consists of: i) the deduction of the equation of motion for the rotation problem of a spherical body with no symmetry, disturbed by a central body; ii) modeling the same problem by including a third-body in the planet-star system; iii) formulation of the concept of “spin-orbit” resonance in which the orbital period of the planet is an integer multiple of the rotation’s period. Topics of dynamical systems (e.g. equilibrium points, chaos, surface sections, etc.) will be included at this stage. In the numerical part simulations are performed with numerical models developed in the previous analytical section. As a first step we consider the orbit of the planet not perturbed by a third-body in the star-planet system. In this case the eccentricity and orbital semi-major axis of the planet are constants. Here the technique of surface sections, widely used in dynamical systems are applied. Next, we consider the action of a third body, developing a more realistic model for planetary rotation. The results in both cases are compared. Since the technique of disturbed surface sections is no longer applicable, we quantitatively evaluate the evolution of the characteristic angles of rotation (e.g. physical libration) by studying the evolution of individual orbits in the dynamically important regions of phase space, the latter obtained in the undisturbed case

Deformation and tidal evolution of close-in planets and satellites using a Maxwell viscoelastic rheology

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Investigation of Ground- and Excited-State Photophysical Properties of 5,10,15,20-Tetra(4-pyridyl)-21H,23H-porphyrin with Ruthenium Outlying Complexes

The present work employs a set of complementary techniques to investigate the influence of outlying Ru(II) groups on the ground- and excited-state photophysical properties of free-base tetrapyridyl porphyrin (H(2)TPyP). Single pulse and, pulse train Z-scan techniques used M association with laser flash photolysis, absorbance and fluorescence spectroscopy, and fluorescence decay measurements, allowed us to conclude that the presence of outlying Ru(II) groups causes significant changes on both electronic structure and vibrational properties of porphyrin. Such modifications take place mainly due to the activation of. nonradiative decay channels responsible for the emission, quenching, as well as by favoring some vibrational modes in the light absorption process, It is also observed that, differently from what happens when the Ru(II) is placed at the center of the macrocycle, the peripheral groups cause an increase of the intersystem crossing processes, probably due to the structural distortion of the ring that implies a worse spin orbit coupling, responsible for the intersystem crossing mechanism.

Exponential depletion of neutral dangling bonds density (D-0) by rare-earth doping in amorphous Si films

In this work we study the effect reduction in the density of dangling bond species D-0 states in rare-earth (RE) doped a-Si films as a function concentration for different RE-specimens. The films a-Si-1_(x) REx, RE=Y3+, Gd3+, Er3+, Lu3+) were prepared by co-sputtering and investigated by electron spin resonance (ESR) and Raman scattering experiments. According to our data the RE-doping reduces the ESR signal intensity of the D-0 states with an exponential dependence on the rare-concentration. Furthermore, the reduction produced by the magnetic rare-earths Gd3+ and Er3+ is remarkably greater than that caused by Y3+ and Lu3+, which led us to suggest an exchange-like coupling between the spin of the magnetic REs3+ and the spin of silicon neutral dangling bonds. (C) 2011 Elsevier B.V. All rights reserved.

First-principles studies of complex magnetism in Mn nanostructures on the Fe(001) surface

The magnetic properties of Mn nanostructures on the Fe(001) surface have been studied using the noncollinear first-principles real space-linear muffin-tin orbital-atomic sphere approximation method within density-functional theory. We have considered a variety of nanostructures such as adsorbed wires, pyramids, and flat and intermixed clusters of sizes varying from two to nine atoms. Our calculations of interatomic exchange interactions reveal the long-range nature of exchange interactions between Mn-Mn and Mn-Fe atoms. We have found that the strong dependence of these interactions on the local environment, the magnetic frustration, and the effect of spin-orbit coupling lead to the possibility of realizing complex noncollinear magnetic structures such as helical spin spiral and half-skyrmion.

Polyelectrolytes and their counterions studied by EPR spectroscopy

In this thesis methods of EPR spectroscopy were used to investigate polyion-counterion interactions in polyelectrolyte solutions. The fact that EPR techniques are local methods is exploited and by employing spin-carrying (i.e., EPR-active) probe ions it is possible to examine polyelectrolytes from the counterions’ point of view. It was possible to gain insight into i) the dynamics and local geometry of counterion attachment, ii) conformations and dynamics of local segments of the polyion in an indirect manner, and iii) the spatial distribution of spin probe ions that surround polyions in solution. Analysis of CW EPR spectra of dianion nitroxide spin probe Fremy’s salt (FS, potassium nitrosodisulfonate) in solutions of cationic PDADMAC polyelectrolyte revealed that FS ions and PDADMAC form transient ion pairs with a lifetime of less than 1 ns. This effect was termed as dynamic electrostatic attachment (DEA). By spectral simulation taking into account the rotational dynamics as a uniaxial Brownian reorientation, also the geometry of the attached state could be characterized. By variation of solvent, the effect of solvent viscosity and permittivity were investigated and indirect information of the polyelectrolyte chain motion was obtained. Furthermore, analysis of CW EPR data also indicates that in mixtures of organic solvent/water PDADMAC chains are preferentially solvated by the organic solvent molecules, while in purely aqueous mixtures the PDADMAC chain segments were found in different conformations depending on the concentration ratio R of FS counterions to PDADMAC repeat units.Broadenings in CW EPR spectra of FS ions were assigned to spin-exchange interaction and hence contain information on the local concentrations and distributions of the counterions. From analysis of these broadenings in terms of a modified cylindrical cell approach of polyelectrolyte theory, radial distribution functions for the FS ions in the different solvents were obtained. This approach breaks down in water above a threshold value of R, which again indicates that PDADMAC chain conformations are altered as a function of R. Double electron-electron resonance (DEER) measurements of FS ions were carried out to probe the distribution of attached counterions along polyelectrolyte chains. For a significant fraction of FS spin probes in solution with a rigid-rod model polyelectrolyte containing charged Ru2+-centers, a bimodal distance distribution was found that nicely reproduced the spacings of direct and next-neighbor Ru2+-centers along the polyelectrolyte: 2.35 and 4.7 nm. For the system of FS/PDADMAC, DEER data could be simulated by assuming a two-state distribution of spin probes, one state corresponding to a homogeneous (3-dimensional) distribution of spin probes in the polyelectrolyte bulk and the other to a linear (1-dimensional) distribution of spin probes that are electrostatically condensed along locally extended PDADMAC chain segments. From this analysis it is suggested that the PDADMAC chains form locally elongated structures of a size of at least ~5 nm.

Synthesis and characterization of new discotic polycyclic aromatic hydrocarbons and related pyrolytic nanostructures

Diskotische Hexa-peri-hexabenzocoronene (HBC) als molekulare, definierte graphitische Substrukturen sind bereits seit langem Gegenstand von Untersuchungen zu der Delokalisierung von π-Elektronen. In dieser Arbeit wurden zusätzlich Platin-Komplexe in das periphere Substitutionsmuster von HBC eingeführt. Dies führte zu einer Verbesserung der Emission von dem angeregten Triplett-Zustand in den Singulett-Grundzustand mit einer zusätzlichen Verlängerung der Lebensdauer des angeregten Zustandes. Zusätzlich erlaubte diese Konfiguration ein schnelles Intersystem-Crossing mittels einer verstärkten Spin-Orbit Kopplung, die sowohl bei tiefen Temperaturen, als auch bei Raumtemperatur exklusiv zu Phosphoreszenz (T1→S0) führte. Das Verständniss über solche Prozesse ist auch essentiell für die Entwicklung verbesserter opto-elektronischer Bauteile. Die Erstellung von exakt definierten molekularen Strukturen, die speziell für spezifische Interaktionen hergestellt wurden, machten eine Inkorporation von hydrophoben-hydrophilen, wasserstoffverbrückten oder elektrostatischen funktionalisierten Einheiten notwendig, um damit den supramolekularen Aufbau zu kontrollieren. Mit Imidazolium-Salzen funktionalisierte HBC Derivate wurden zu diesem Zwecke hergestellt. Eine interessante Eigenschaft dieser Moleküle ist ihre Amphiphilie. Dies gestattete die Untersuchung ihrer Eigenschaften in einem polaren Solvens und sowohl der Prozessierbarkeit als auch der Faserbildung auf Siliziumoxid-Trägern. Abhängig vom Lösungsmittel und der gewählten Konditionen konnten hochkristalline Fasern erhalten werden. Durch eine Substitution der HBCs mit langen, sterisch anspruchsvollen Seitenketten, konnte durch eine geeignete Prozessierung eine homöotrope Ausrichtung auf Substraten erreicht werden, was dieses Material interessant für photovoltaische Applikationen macht. Neuartige Polyphenylen-Metall-Komplexe mit diskotischen, linearen und dendritischen Geometrien wurden mittels einer einfachen Reaktion zwischen Co2(CO)8 und Ethinyl-Funktionalitäten in Dichlormethan hergestellt. Nach der Pyrolyse dieser Komplexe ergaben sich unterschiedliche Kohlenstoff-Nanopartikel, inklusive Nanoröhren, graphitischen Nanostäben und Kohlenstoff/Metall Hybrid Komplexe, die durch Elektronenmikroskopie untersucht wurden. Die resultierenden Strukturen waren dabei abhängig von der Zusammensetzung und Struktur der Ausgangssubstanzen. Anhand dieser Resultate ergeben sich diverse Möglichkeiten, um den Mechanismus, der zur Herstellung graphitischer Nanopartikel führt, besser zu verstehen.