CASPT2 Study of the Potential Energy Surface of the HSO(2) System

The importance of the HSO(2) system in atmospheric and combustion chemistry has motivated several works dedicated to the study of associated structures and chemical reactions. Nevertheless controversy still exists in connection with the reaction SH + O(2) -> H + SO(2) and also related to the role of the HSOO isomers in the potential energy surface (PES). Here we report high-level ab initio calculation for the electronic ground state of the HSO(2) system. Energetic, geometric, and frequency properties for the major stationary states of the PES are reported at the same level of calculations:,CASPT2/aug-cc-pV(T+d)Z. This study introduces three new stationary points (two saddle points and one minimum). These structures allow the connection of the skewed HSOOs and the HSO(2) minima defining new reaction paths for SH + O(2) -> H + SO(2) and SH + O(2) -> OH + SO. In addition, the location of the HSOO isomers in the reaction pathways have been clarified.

Exploring new molecular species on the (1)[H, Se, F] singlet potential energy surface: Energetics, structures, IR spectra, and heats of formation

Structural, energetic, and vibrational properties of new molecular species, HSeF and HFSe, the associated transition state, and dissociation fragments are investigated using a state-of-the-art theoretical approach, CCSD(T)/CBS. HSeF is a normal covalently bonded molecule 38.98 kcal mol (1) more stable than the complex HF-Se, which shows an unusual structure with a central fluorine atom and a bond angle of 101.8 degrees.A barrier (Delta G(#)) of 49.01 kcal mol (1) separates the two species. Vibrational frequencies are also quite distinct. Heats of formation are evaluated for the diatomic fragments and HSeF. Final Delta(f)H values depend on the experimental accuracy of those of Se(g) and H(2)Se. (c) 2009 Elsevier B.V. All rights reserved.

Isomers on the [H, S(2), Cl] potential energy surface: A high level investigation

This study reports a systematic state-of-the-art characterization of new sulfur-chlorine species on the [H, S(2), Cl] potential energy surface. Coupled cluster theory singles and doubles with perturbative contributions of connected triples, using the series of correlation consistent basis sets with extrapolations to the complete basis set limit (CBS), were employed to quantify the energetic quantities involved in the isomerization processes on this surface. The structures and vibrational frequencies are unique for some species and represent the most accurate investigation to date. These molecules are potentially a new route of coupling the sulfur and chlorine chemistries in the atmosphere, and conditions of high concentration of H(2)S (HS) like in volcanic eruptions might contribute to their formation. Also an assessment of the MP2/CBS approach relative to CCSD(T)/CBS provides insights on the expected performance of MP2/CBS on the characterization of polysulfides, and also of more complex systems containing disulfide bridges. (C) 2009 Elsevier B.V. All rights reserved.

The reaction of methyl radical with nitrogen atom on the triplet potential energy surface: A CCSD(T)/CBS characterization

CCSD(T)/cc-pVnZ (n = D, T, Q) calculations followed by extrapolations to the CBS limit are used to characterize stationary states of species participating in the N((4)S) + CH(3) (2A ``) reaction on the triplet PES. A mechanistic model is investigated and reaction rates are computed for every step and the overall reaction. Our best CBS estimate (1.93 x 10(10) cm(3) molecule(1) s(1)) for the overall rate constant leading to the formation of H(2)CN + H compares well with the experimental values (8.5 x 10 (11) and 1.3 x 10(10) cm(3) molecule(1) s(1)), thus reducing significantly the discrepancy of a previous theoretical result (9.1 x 10(12) cm(3) molecule(1) s(1)). (C) 2008 Elsevier B.V. All rights reserved.

Proteomic analysis of dorsolateral prefrontal cortex indicates the involvement of cytoskeleton, oligodendrocyte, energy metabolism and new potential markers in schizophrenia

Schizophrenia is likely to be a consequence of serial alterations in a number of genes that, together with environmental factors, will lead to the establishment of the illness. The dorsolateral prefrontal cortex (Brodmann`s Area 46) is implicated in schizophrenia and executes high functions such as working memory, differentiation of conflicting thoughts, determination of right and wrong concepts, correct social behavior and personality expression. We performed a comparative proteome analysis using two-dimensional gel electrophoresis of pools from 9 schizophrenia and 7 healthy control patients` dorsolateral prefrontal cortex aiming to identify, by mass spectrometry, alterations in protein expression that could be related to the disease. In schizophrenia-derived samples, our analysis revealed 10 downregulated and 14 upregulated proteins. These included alterations previously implicated in schizophrenia, such as oligodendrocyte-related proteins (myelin basic protein and transferrin), as well as malate dehydrogenase, aconitase, ATP synthase subunits and cytoskeleton-related proteins. Also, six new putative disease markers were identified, including energy metabolism, cytoskeleton and cell signaling proteins. Our data not only reinforces the involvement of proteins previously implicated in schizophrenia, but also suggests new markers, providing further information to foster the comprehension of this important disease. (C) 2008 Elsevier Ltd. All rights reserved.

New Molecular Species of Potential Interest to Atmospheric Chemistry: Isomers on the [H, S(2), Br] Potential Energy Surface

This work reports a state-of-the-art theoretical characterization of four new sulfur-bromine species and five transition states on the [H, S(2), Br] potential energy surface. Our highest level theoretical approach employed the method coupled cluster singles and doubles with perturbative contributions of connected triples, CCSD(T), along with the series of correlation-consistent basis sets and with extrapolation to the complete basis set (CBS) limit in the optimization of the geometrical parameters and to quantify the energetic quantities. The structural and vibrational frequencies here reported are unique and represent the most accurate investigation to date of these species. The global minimum corresponds to a skewed structure HSSBr with a disulfide bond; this is followed by a pyramidal-like structure, SSHBr, 18.85 kcal/mol above the minimum. Much higher in energy, we found another skewed structure, HSBrS (50.29 kcal/mol), with one S-Br dative-type bond, and another pyramidal-like one, HBrSS (109.80 kcal/mol), with two S-Br dative-type bonds. The interconversion of HSSBr into SSHBr can occur via a transfer of either the hydrogen or the bromine atom but involves a very high barrier of about 43 kcal/mol. These molecules are potentially a new route of coupling the sulfur and bromine chemistry in the atmosphere, and conditions of high concentration of H(2)S like in volcanic eruptions might contribute to their formation. We note that HSSBr can act as a reservoir molecule for the reaction between the radicals HSS and Br. Also, an assessment of the methods DFT/B3LYP/CBS and MP2/CBS relative to CCSD(T)/CBS provides insights on the expected performance of these methods on the characterization of polysulfides and also of more complex systems containing disulfide bridges.

The energy cycle and structural evolution of cyclones over southeastern South America in three case studies

In this paper, the Lorenz energy cycle over a limited area was applied for three cyclones with different origins and evolutions, where each of them was formed in an important cyclogenetic region near southeastern South America. The synoptic conditions and energetics were analyzed during each system`s life cycle and showed important relationships between their energy cycle and the evolution of their vertical structure. In the case of the weak baroclinic cyclone which formed on Brazil`s south-southeastern coast, the analysis showed that it originated through a midlevel cutoff low with contribution from barotropic instability. Its evolution would indicate potential transition to a hybrid system if the convective activity were stronger. The system that occurred in the La Plata River mouth had features of an oceanic bomb-type cyclogenesis and showed an important contribution from the available potential energy generation term through the latent heat release by the convection. Meanwhile, the system of the southern Argentina coast presented a classical baroclinic development of extratropical cyclogenesis in the energy cycle, from the wave amplification up to the final occlusion of the associated frontal system. These analyses revealed that the development of some cyclones that occur in eastern South America can present different mechanisms that are not related to the classical extratropical cyclogenesis.

An accelerating cosmology without dark energy

The negative pressure accompanying gravitationally-induced particle creation can lead to a cold dark matter (CDM) dominated, accelerating Universe (Lima et al. 1996 [1]) without requiring the presence of dark energy or a cosmological constant. In a recent study, Lima et al. 2008 [2] (LSS) demonstrated that particle creation driven cosmological models are capable of accounting for the SNIa observations [3] of the recent transition from a decelerating to an accelerating Universe, without the need for Dark Energy. Here we consider a class of such models where the particle creation rate is assumed to be of the form Gamma = beta H + gamma H(0), where H is the Hubble parameter and H(0) is its present value. The evolution of such models is tested at low redshift by the latest SNe Ia data provided by the Union compilation [4] and at high redshift using the value of z(eq), the redshift of the epoch of matter - radiation equality, inferred from the WMAP constraints on the early Integrated Sachs-Wolfe (ISW) effect [5]. Since the contributions of baryons and radiation were ignored in the work of LSS, we include them in our study of this class of models. The parameters of these more realistic models with continuous creation of CDM are constrained at widely-separated epochs (z(eq) approximate to 3000 and z approximate to 0) in the evolution of the Universe. The comparison of the parameter values, {beta, gamma}, determined at these different epochs reveals a tension between the values favored by the high redshift CMB constraint on z(eq) from the ISW and those which follow from the low redshift SNIa data, posing a potential challenge to this class of models. While for beta = 0 this conflict is only at less than or similar to 2 sigma, it worsens as beta increases from zero.

Energy substrate utilization during nightly vocal activity in three species of Scinax (Anura/Hylidae)

Anuran amphibians exhibit different patterns of energy substrate utilization that correlate with the intensity of vocal and locomotor activities. Given the remarkable differences among species in breeding and feeding strategies, and the different ways energy is used in the whole animal, the suggested correlations between calling and locomotor behavior and the level of energy substrates in the muscles responsible for such activities are more complex than previously reported. We explored the relationships between calling and locomotor behavior and energy supply to trunk and hindlimb muscles, respectively, within the ecologically diverse tree-frog genus Scinax. Specifically, we measured the relative amount of carbohydrates and lipids in these two groups of muscles, and in the liver of three species of Scinax that differ in vocal and locomotor performance, and compared our results with those of two other species for which comparable data are available. We also compared the contents of lipids and carbohydrates of conspecific males collected at the beginning and after 4 h of calling activity. The stomach content to potential feeding opportunities across species was also assessed in both groups of males. Scinax hiemalis and S. rizibilis exhibit comparatively low and episodic calling during long periods of activity whereas S. crospedospilus calls at higher rates over shorter periods. Male S. hiemalis had highest levels of trunk muscle glycogen followed by those of S. rizilbilis and S. crospedospilus, respectively. There was no correlation between total lipid content in trunk muscle and calling rate among different species, suggesting that other metabolic aspects may be responsible for the energetic support for vocal activity. The levels of lipids and carbohydrates in trunk and hindlimb muscles and liver of males collected at the beginning and 4 h into the calling period were similar across species, so the extent of energetic reserves does not appear to constrain vocal or locomotor activity. Finally, we found exceptionally high levels of carbohydrates and lipids in the liver of S. rizibilis, a trait perhaps related to a long and demanding breeding period.

The potential for first-generation ethanol production from sugarcane

Ethanol production from sugarcane, mainly in Brazil, on the basis of first-generation technology (22.5 billion liters, in 2007/2008 season, in 3.4 million hectares) replaces 1% of the gasoline used in the world today and is highly competitive in economic terms with ethanol produced from other crops in the USA and Europe. In this paper we discuss the potential for sugarcane ethanol expansion from two angles: (1) productivity gains which would allow greater production in the same area and (2) geographical expansion to larger areas. The potential of first-generation technology for the production of ethanol from sugarcane is far from being exhausted. There are gains in productivity of approximately a factor of two from genetically modified varieties and a geographical expansion by a factor of ten of the present level of production in many sugar-producing countries. The replacement of 10% of the gasoline used in the world by ethanol from sugarcane seems possible before second-generation technology reaches technological maturity and possibly economic competitiveness. (C) 2009 Society of Chemical Industry and John Wiley & Sons, Ltd

Canonical quantum potential scattering theory

A new formulation of potential scattering in quantum mechanics is developed using a close structural analogy between partial waves and the classical dynamics of many non-interacting fields. Using a canonical formalism we find nonlinear first-order differential equations for the low-energy scattering parameters such as scattering length and effective range. They significantly simplify typical calculations, as we illustrate for atom-atom and neutron-nucleus scattering systems. A generalization to charged particle scattering is also possible.

An imaginary potential with universal normalization for dissipative processes in heavy-ion reactions

In this work we present new coupled channel calculations with the Sao Paulo potential (SPP) as the bare interaction, and an imaginary potential with system and energy independent normalization that has been developed to take into account dissipative processes in heavy-ion reactions. This imaginary potential is based on high-energy nucleon interaction in nuclear medium. Our theoretical predictions for energies up to approximate to 100 MeV/nucleon agree very well with the experimental data for the p, n + nucleus, (16)O + (27)Al, (16)O + (60)Ni, (58)Ni + (124)Sn, and weakly bound projectile (7)Li + (120)Sn systems. (C) 2008 Elsevier B.V. All rights reserved.

Observational constraints on holographic tachyonic dark energy in interaction with dark matter

We discuss an interacting tachyonic dark energy model in the context of the holographic principle. The potential of the holographic tachyon field in interaction with dark matter is constructed. The model results are compared with CMB shift parameter, baryonic acoustic oscilations, lookback time and the Constitution supernovae sample. The coupling constant of the model is compatible with zero, but dark energy is not given by a cosmological constant.

On the lower bound on the exchange-correlation energy in two dimensions

We study the properties of the lower bound on the exchange-correlation energy in two dimensions. First we review the derivation of the bound and show how it can be written in a simple density-functional form. This form allows an explicit determination of the prefactor of the bound and testing its tightness. Next we focus on finite two-dimensional systems and examine how their distance from the bound depends on the system geometry. The results for the high-density limit suggest that a finite system that comes as close as possible to the ultimate bound on the exchange-correlation energy has circular geometry and a weak confining potential with a negative curvature. (c) 2009 Elsevier B.V. All rights reserved.

CARBON CREDITS AND ENERGY EFFICIENCY

International carbon credit markets are based in differences between developing and developed countries greenhouse gases emissions mitigation costs and technological limits faced by developed countries. Potential of energy efficiency measures to reduce fossil fuel usage in Brazilian industrial segments is assessed, and analysis of such potentials singles out those segments and regions more apt to generate carbon credits through Clean Development Mechanism (CDM) projects. Though there are currently few Brazilian CDM projects, their number may be significantly increased, which is a positive outcome. For this purpose, it is crucial that energy conservation programs estimate how CDM may improve their economic competitiveness.