Low-energy three-body charge transfer reactions with Coulomb interaction in the final state

Three-body charge transfer reactions with Coulomb interaction in the final state are considered within the framework of coordinate-space integro-differential Faddeev-Hahn-type equations within two- and six-state close-coupling approximations. The method is employed to study direct muon transfer in low-energy collisions of the muonic hydrogen H-mu by helium (He2+) and lithium (Li3+) nuclei. The experimentally observed isotopic dependence is reproduced.

The energy landscape for solvent dynamics in electron transfer reactions: A minimalist model

Energy fluctuations of a solute molecule embedded in a polar solvent are investigated to depict the energy landscape for solvation dynamics. The system is modeled by a charged molecule surrounded by two layers of solvent dipolar molecules with simple rotational dynamics. Individual solvent molecules are treated as simple dipoles that can point toward or away from the central charge (Ising spins). Single-spin-flip Monte Carlo kinetics simulations are carried out in a two-dimensional lattice for different central charges, radii of outer shell, and temperatures. By analyzing the density of states as a function of energy and temperatures, we have determined the existence of multiple freezing transitions. Each of them can be associated with the freezing of a different layer of the solvent. (C) 2002 American Institute of Physics.

Smooth landscape solvent dynamics in electron transfer reactions

Solvent effects play a major role in controlling electron-transfer reactions. The solvent dynamics happens on a very high-dimensional surface, and this complex landscape is populated by a large number of minima. A critical problem is to understand the conditions under which the solvent dynamics can be represented by a single collective reaction coordinate. When this unidimensional representation is valid, one recovers the successful Marcus theory. In this study the approach used in a previous work [V. B. P. Leite and J. N. Onuchic; J. Phys. Chem. 100, 7680 (1996)] is extended to treat a more realistic solvent model, which includes energy correlation. The dynamics takes place in a smooth and well behaved landscape. The single shell of solvent molecules around a cavity is described by a two-dimensional system with periodic boundary conditions with nearest neighbor interaction. It is shown how the polarization-dependent effects can be inferred. The existence of phase transitions depends on a factor y proportional to the contribution from the two parameters of the model. For the present model, γ suggests the existence of weak kinetic phase transitions, which are used in the analysis of solvent effects in charge-transfer reactions. © 1999 American Institute of Physics.

Coordinate-space Faddeev-Hahn-type approach to three-body charge-transfer reactions involving exotic particles

Low-energy muon-transfer cross sections and rates in collisions of muonic atoms with hydrogen isotopes are calculated using a six-state close-coupling approximation to coordinate-space Faddeev-Hahn-type equations. In the muonic case satisfactory results are obtained for all hydrogen isotopes and the experimentaly observed strong isotopic dependence of transfer rates is also reproduced. A comparison with results of other theoretical and available experimental works is presented. The present model also leads to good transfer cross sections in the well-understood problem of antihydrogen formation in antiproton-positronium collision.

Oxygen Atom Transfer Reactions from Mimoun Complexes to Sulfides and Sulfoxides. A Bonding Evolution Theory Analysis

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Statistics and kinetics of single-molecule electron transfer dynamics in complex environments: A simulation model study

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

Dynamical calculation of direct muon-transfer rates from thermalized muonic hydrogen to C6+ and O8+

Moun-transfer reactions from muonic hydrogen to carbon and oxygen nuclei employing a full quantum-mechanical few-body description of rearrangement scattering were studied by solving the Faddeev-Hahn-type equations using close-coupling approximation. The application of a close-coupling-type ansatz led to satisfactory results for direct muon-transfer reactions from muonic hydrogen to C6+ and O8+.

Electrochemical Redox Behavior of Omeprazole Using a Glassy Carbon Electrode

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A few-body treatment of low energy atomic collisions involving exotic particles

Faddeev-type equations are applied to three-charged particle systems. The rather satisfactory results are obtained for low energy e(+)H elastic scattering and muonic transfer reactions. The cross sections for antihydrogen formation from antiproton-positronium collisions are calculated using a six state model (Ps[1s2s2p], (H) over bar[1s2s2p]).

Dinâmica de modelos minimalistas de solvente em reações de transferência de elétrons: aplicação à experimentos de única molécula

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Complexos cofaciais de dirutênio contendo haletos em ponte e fosfinas como ligantes: estudos espectrais, eletroquímicos e de reatividade

Pós-graduação em Química - IQ

Screening the toxicity and biodegradability of petroleum hydrocarbons by a rapid colorimetric method

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A theoretical study on the gas phase reactions of the anions NbO3-, NbO5-, and NbO2(0H)(2)(-) with H2O and O-2

The potential energy surfaces at the singlet (s) and the triplet (t) electronic states associated with the gas-phase ion/molecule reactions of NbO3-, NbO5-, and NbO2(OH)(2)(-) with H2O and O-2 have been investigated by means of DFT calculations at the B3LYP level. An analysis of the results points out that the most favorable reactive channel comprises s-NbO3- reacting with H2O to give an ion-molecule complex s-NbO3(H2O)without a barrier. From this minima, an intramolecular hydrogen transfer takes place between the incoming water molecule and an oxygen atom of the NbO3- fragment to render the most stable minimum, s-NbO2(OH)(2)(-). This oxyhydroxide system reacts with O-2 along a barrierless process to obtain the triplet t-NbO4(OH)(2)(-)-A intermediate, and the crossing point, CP1, between s and t electronic states has been characterized. The next step is the hydrogen-transfer process between the oxygen atom of a hydroxyl group and the one adjacent oxygen atom to render a minimum with the two OH groups near each other, t-NbO4(OH)(2)(-)-B. From this point, the last hydrogen migration takes place, to obtain the product complex, t-NbO5(H2O)(-), that can be connected with the singlet separated products, s-NbO5- and H2O. Therefore, a second crossing point, CP2, has been localized. The nature of the chemical bonding of the key minima (NbO3-, NbO2(OH)(2)(-), NbO4(OH)(2)(-)-B, and NbO5-) in both electronic states of the reaction and an interaction with O-2 has been studied by topological analysis of Becke-Edgecombe electron-localization function (ELF) and atoms-in-molecules (AIM) methodology. The niobium-oxygen interactions are characterized as unshared-electron (ionic) interactions and some oxygen-oxygen interactions as protocovalent bonds.

Electron migration in DNA matrix: an electron transfer reaction

Este artigo apresenta uma área de pesquisa atual, ativa e interessante. Descreve a investigação da química de transferência de elétrons (TE) de um modo geral e resultados de TE em DNA em particular. Dois intercalantes de DNA foram utilizados: Ethidium Bromide como doador (D) e Methyl-viologen como receptor (A), o primeiro intercala-se entre as bases do DNA e o último na sua superfície. Utilizando o modelo de Perrin e medidas de Supressão de Fluorescência obteve-se a distância de migração do elétron; aqui a distância foi considerada o espaçamento linear entre as moléculas de doador e receptor ao longo da molécula de DNA. O valor determinado foi de 22,6 ± 1,1 angstrons e o número de pares de bases entre doador e receptor de 6,6. Na literatura os valores encontrados foram de 26 angstrons e de quase 8 pares de bases. Considera-se que a transferência de elétrons em DNA seja mediada através das interações através do espaço entre os elétrons do tipo p contido nos pares de bases.

The University and its libraries: Reactions and resistance to scientific publishers

This paper addresses the relationship of copyright and the right of universities on scientific production. Information and Communication Technologies (ICTs) are causing many changes in the system of scientific communication, such as the creation of Institutional Repositories that aim to gather scientific production in digital format. The University needs quicker ways of spreading academic production and many questions are emerging due to contexts such as the Open Access movement. Thus, this paper questions the positioning of Universities, especially Public Universities, which despite having policies related to intellectual property to protect the transferring forms of research results to society; many times do not have a positioning or a mechanism that regulates the self-deposit of scientific production in these Institutional Repositories. In order to develop this paper, the following issues are addressed: lack of interest of the University in storing scientific production; reports on the relationship of the library with scientific publishing houses; the participation of faculty members and students in supporting the Free Access movement; and initiatives aimed at greater flexibility of copyright to the context of scientific production. In order to follow the development of these issues at international level, it was opted for qualitative research with non-participating direct observation to carry out the identification and description of copyright policy of important publishers from the ROMEO SHERPA site; therefore, it can be observed that there are changes regarding the publishers' flexibility before self-archiving of authors in open access institutional repositories in their universities. Given this scenario, we presente reflections and considerations that involve the progress and mainly the integration of the University and its faculty members; the institution should recommend and guide its faculty members not to transfer their copyrights, but to defend their right of copy to Institutional Repositories along with Publishing Houses.