Ab Initio Analysis of Monomers and Dimers of Trialkylphosphine Oxides: Structural and Thermodynamic Stability

Structural and thermodynamic stabilities of monomers and dimers of trialkylphosphine oxides (TRPO) were Studied using quantum chemistry calculations. Density functional theory calculations were carried Out and the structures Of four TRPO have been determined: TMPO (methyl; R = CH(3)), TEPO (ethyl; R = CH(3)CH(2)), TBPO (n-butyl; R = CH(3)(CH(2))(3)), and TOPO (n-octyl; R = CH(3)(CH(2))(7)). TRPO homodimers were investigated considering two isomeric possibilities for each dimer. Relative binding energies and the enthalpic and entropic contributions to the Gibbs free energy were Calculated for all dimers. The formation of dimers from the individual monomeric TRPO species as a function of temperature was also analyzed. (C) 2008 Wiley Periodicals, Inc. Int J Quantum Chem 109: 250-258, 2009

Axial ligand influence on geometries, charge distributions and electronic structures of iron tetraazamacrocycle [Fe((II))TIM(X)(Y)](2+) complexes assessed by Density Functional Theory

We employed the Density Functional Theory along with small basis sets, B3LYP/LANL2DZ, for the study of FeTIM complexes with different pairs of axial ligands (CO, H(2)O, NH(3), imidazole and CH(3)CN). These calculations did not result in relevant changes of molecular quantities as bond lengths, vibrational frequencies and electronic populations supporting any significant back-donation to the carbonyl or acetonitrile axial ligands. Moreover, a back-donation mechanism to the macrocycle cannot be used to explain the observed changes in molecular properties along these complexes with CO or CH(3)CN. This work also indicates that complexes with CO show smaller binding energies and are less stable than complexes with CH(3)CN. Further, the electronic band with the largest intensity in the visible region (or close to this region) is associated to the transition from an occupied 3d orbital on iron to an empty pi* orbital located at the macrocycle. The energy of this Metal-to-Ligand Charge Transfer (MLCT) transition shows a linear relation to the total charge of the macrocycle in these complexes as given by Mulliken or Natural Population Analysis (NPA) formalisms. Finally, the macrocycle total charge seems to be influenced by the field induced by the axial ligands. (C) 2011 Elsevier Ltd. All rights reserved.

Modelagem molecular na caracterização eletrônica de oligopeptídeos e na descrição quântica da interação fármaco-receptor

In this dissertation, the theoretical principles governing the molecular modeling were applied for electronic characterization of oligopeptide α3 and its variants (5Q, 7Q)-α3, as well as in the quantum description of the interaction of the aminoglycoside hygromycin B and the 30S subunit of bacterial ribosome. In the first study, the linear and neutral dipeptides which make up the mentioned oligopeptides were modeled and then optimized for a structure of lower potential energy and appropriate dihedral angles. In this case, three subsequent geometric optimization processes, based on classical Newtonian theory, the semi-empirical and density functional theory (DFT), explore the energy landscape of each dipeptide during the search of ideal minimum energy structures. Finally, great conformers were described about its electrostatic potential, ionization energy (amino acids), and frontier molecular orbitals and hopping term. From the hopping terms described in this study, it was possible in subsequent studies to characterize the charge transport propertie of these peptides models. It envisioned a new biosensor technology capable of diagnosing amyloid diseases, related to an accumulation of misshapen proteins, based on the conductivity displayed by proteins of the patient. In a second step of this dissertation, a study carried out by quantum molecular modeling of the interaction energy of an antibiotic ribosomal aminoglicosídico on your receiver. It is known that the hygromycin B (hygB) is an aminoglycoside antibiotic that affects ribosomal translocation by direct interaction with the small subunit of the bacterial ribosome (30S), specifically with nucleotides in helix 44 of the 16S ribosomal RNA (16S rRNA). Due to strong electrostatic character of this connection, it was proposed an energetic investigation of the binding mechanism of this complex using different values of dielectric constants (ε = 0, 4, 10, 20 and 40), which have been widely used to study the electrostatic properties of biomolecules. For this, increasing radii centered on the hygB centroid were measured from the 30S-hygB crystal structure (1HNZ.pdb), and only the individual interaction energy of each enclosed nucleotide was determined for quantum calculations using molecular fractionation with conjugate caps (MFCC) strategy. It was noticed that the dielectric constants underestimated the energies of individual interactions, allowing the convergence state is achieved quickly. But only for ε = 40, the total binding energy of drug-receptor interaction is stabilized at r = 18A, which provided an appropriate binding pocket because it encompassed the main residues that interact more strongly with the hygB - C1403, C1404, G1405, A1493, G1494, U1495, U1498 and C1496. Thus, the dielectric constant ≈ 40 is ideal for the treatment of systems with many electrical charges. By comparing the individual binding energies of 16S rRNA nucleotides with the experimental tests that determine the minimum inhibitory concentration (MIC) of hygB, it is believed that those residues with high binding values generated bacterial resistance to the drug when mutated. With the same reasoning, since those with low interaction energy do not influence effectively the affinity of the hygB in its binding site, there is no loss of effectiveness if they were replaced.

Propriedades ópticas de nanocristais de SiGe: efeitos de dopagem e desordem

We have used ab initio calculations to investigate the electronic structure of SiGe based nanocrystals (NC s). This work is divided in three parts. In the first one, we focus the excitonic properties of Si(core)/Ge(shell) and Ge(core)/Si(shell) nanocrystals. We also estimate the changes induced by the effect of strain the electronic structure. We show that Ge/Si (Si/Ge) NC s exhibits type II confinement in the conduction (valence) band. The estimated potential barriers for electrons and holes are 0.16 eV (0.34 eV) and 0.64 eV (0.62 eV) for Si/Ge (Ge/Si) NC s. In contradiction to the expected long recombination lifetimes in type II systems, we found that the recombination lifetime of Ge/Si NC s (τR = 13.39μs) is more than one order of magnitude faster than in Si/Ge NC s (τR = 191.84μs). In the second part, we investigate alloyed Si1−xGex NC s in which Ge atoms are randomly positioned. We show that the optical gaps and electron-hole binding energies decrease linearly with x, while the exciton exchange energy increases with x due to the increase of the spatial extent of the electron and hole wave functions. This also increases the electron-hole wave functions overlap, leading to recombination lifetimes that are very sensitive to the Ge content. Finally, we investigate the radiative transitions in Pand B-doped Si nanocrystals. Our NC sizes range between 1.4 and 1.8 nm of diameters. Using a three-levels model, we show that the radiative lifetimes and oscillator strengths of the transitions between the conduction and the impurity bands, as well as the transitions between the impurity and the valence bands are strongly affected by the impurity position. On the other hand, the direct conduction-to-valence band decay is practically unchanged due to the presence of the impurity

Kondo-attractive-Hubbard model for the ordering of local magnetic moments in superconductors

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

Activity and characterization by XPS, HR-TEM, Raman spectroscopy, and BET surface area of CuO/CeO2-TiO2 catalysts

Structural and textural studies of a CuO/TiO2 System modified by cerium oxide were conducted using Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and N-2 absorption (BET specific surface area). The introduction of a minor amount of CeO2 (Ce0.09Ti0.82O1.91CU0.09 sample) resulted in a material with the maximum surface area value. The results of Raman spectroscopy revealed the presence of only two crystalline phases, TiO2 anatase and CeO2 cerianite, with well-dispersed copper species. TEM micrographs showed a trend toward smaller TiO2 crystallites when the cerium oxide content was increased. The XPS analysis indicated the rise of a second peak in Ti 2p spectra with the increasing amount of CeO2 located at higher binding energies than that due to the Till in a tetragonal symmetry. The CuO/TiO2 system modified by CeO2 displayed a superior performance for methanol dehydrogenation than the copper catalyst supported only on TiO2 or CeO2.

X-ray photoelectron spectroscopy, x-ray absorption spectroscopy, and x-ray diffraction characterization of CuO-TiO2-CeO2 catalyst system

X-ray photoelectron spectroscopy (XPS), x-ray diffraction (XRD), and x-ray absorption spectroscopy (XAS) techniques have been applied to characterize the surface composition and structure of a series of CuO-TiO2-CeO2 catalysts. For a small loading of cerium, ceria was mainly dispersed on the titania surface and a minor amount of CeO2 crystallite appeared. At higher loading of cerium, the CeO2 phase increased and the atomic Ce/Ti ratio values were smaller than the nominal composition, as a consequence of cerium agglomeration. This result suggests that only a fraction of cerium can be spread on the titania surface. For titanium-based mixed oxide, we observed that cerium is found as Ce3+ uniquely on the surface. The atomic Cu/(Ce+Ti) ratio values showed no influence from cerium concentration on the dispersion of copper, although the copper on the surface was shown to be dependent on the cerium species. For samples with a high amount of cerium, XPS analysis indicated the raise of second titanium species due cerium with spin-orbit components at higher binding energies than those presented by Ti4+ in a tetragonal structure. The structural results obtained by XAS are consistent with those obtained by XRD and XPS. (C) 2001 American Vacuum Society.

Scaling in few-body nuclear physics

The nuclear matter calculations with realistic nucleon-nucleon potentials present a general scaling between the nucleon-nucleus binding energy, the corresponding saturation density, and the triton binding energy. The Thomas-Efimov three-body effect implies in correlations among low-energy few-body and many-body observables. It is also well known that, by varying the short-range repulsion, keeping the two-nucleon information (deuteron and scattering) fixed, the four-nucleon and three-nucleon binding energies lie on a very narrow band known as a Tjon line. By looking for a universal scaling function connecting the proper scales of the few-body system with those of the many-body system, we suggest that the general nucleus-nucleon scaling mechanism is a manifestation of a universal few-body effect.

Triatomic states in ultracold gases

We study the trajectory of Efimov states for a trapped three-boson system when the two-body scattering length a is changed. We show that these states follow the route virtual-bound-continuum resonance state when a is varied, respectively, from large positive to negative values. For a < 0, we include the triatomic continuum resonance effect to extend the three-body recombination length for trap temperatures greater than zero. For a > 0, we predict trimer binding energies based on the recombination length and the two-body scattering length.

Collision of positronium with atoms, molecules and ions using a modified coupled-channel framework

Scattering of positronium (Ps) from atoms (H, He, Ne, Ar), molecule (H(2)) and ion (He(+)) have been investigated using a coupled-channel (CC) formalism with a regularised non-local exchange potential. The advantage of using such a regularized exchange potential in the close-coupling formalism and the normalizability aspect of the solution at low energies with a minimum effective coupling are discussed. Results for the elastic and total scattering cross-sections, resonance and binding energies in Ps-H, and pick-off annihilation results in Ps-He are found to be in excellent agreement with measurements and variational predictions. (C) 2000 Elsevier B.V. B.V. All rights reserved.

The few scales of nuclei and nuclear matter

The well-known correlations of low-energy three and four-nucleon observables with a typical three-nucleon scale (e.g., the Tjon line) is extended to light nuclei and nuclear matter. Evidence for the scaling between light nuclei binding energies and the triton one are pointed out. We argue that the saturation energy and density of nuclear matter are correlated to the triton binding energy. The available systematic nuclear matter calculations indicate a possible band structure representing these correlations. (c) 2006 Elsevier B.V. All rights reserved.

S-, P- and D-wave resonances in positronium-sodium and positronium-potassium scattering

Scattering of positronium (Ps) by sodium and potassium atoms has been investigated employing a three-Ps-state coupled-channel model with Ps(ls,2s,2p) states using a time-reversal-symmetric regularized electron-exchange model potential fitted to reproduce accurate theoretical results for PsNa and PsK binding energies. We find a narrow S-wave singlet resonance at 4.58 eV of width 0.002 eV in the Ps-Na system and at 4.77 eV of width 0.003 eV in the Ps-K system. Singlet P-wave resonances in both systems are found at 5.07 eV of width 0.3 eV. Singlet D-wave structures are found at 5.3 eV in both systems. We also report results for elastic and Ps-excitation cross sections for Ps scattering by Na and K.

Three- and Four-Nucleon Bound States in Three Dimensions, Without PW Decomposition

A brief review of a three-dimensional (3D) numerical method to solve few-nucleon bound and scattering states, without the standard partial-wave (PW) decomposition, is presented. The approach is applied to three-and four-nucleon bound states, by considering the solutions of the corresponding Faddeev-Yakubovsky (FY) integral equations in momentum space. Realistic spin-isospin dependent 3D and PW formalism are presented for the alpha particle and the triton binding energies, with numerical results given in both schemes for comparison.

Constraints on two-neutron separation energy in the Borromean C-22 nucleus

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

Stochastic variational approach applied to 2, 3 and 4 alpha particles

A stochastic variational method is applied to calculate the binding energies and root-mean-square radii of 2, 3 and 4 alpha particles using an S-wave Ali-Bodmer potential. The results agree with other calculations. We discuss the application of the present method to study the universality in weakly-bound three and four-body systems in the context of ultracold atomic traps.