A teoria do funcional da densidade na caracterização de fases intermetálicas ordenadas

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

Correspondence between the one-loop three-point vertex and the Y and Delta electric resistor networks

Different mathematical methods have been applied to obtain the analytic result for the massless triangle Feynman diagram yielding a sum of four linearly independent (LI) hypergeometric functions of two variables F-4. This result is not physically acceptable when it is embedded in higher loops, because all four hypergeometric functions in the triangle result have the same region of convergence and further integration means going outside those regions of convergence. We could go outside those regions by using the well-known analytic continuation formulas obeyed by the F-4, but there are at least two ways we can do this. Which is the correct one? Whichever continuation one uses, it reduces a number of F-4 from four to three. This reduction in the number of hypergeometric functions can be understood by taking into account the fundamental physical constraint imposed by the conservation of momenta flowing along the three legs of the diagram. With this, the number of overall LI functions that enter the most general solution must reduce accordingly. It remains to determine which set of three LI solutions needs to be taken. To determine the exact structure and content of the analytic solution for the three-point function that can be embedded in higher loops, we use the analogy that exists between Feynman diagrams and electric circuit networks, in which the electric current flowing in the network plays the role of the momentum flowing in the lines of a Feynman diagram. This analogy is employed to define exactly which three out of the four hypergeometric functions are relevant to the analytic solution for the Feynman diagram. The analogy is built based on the equivalence between electric resistance circuit networks of types Y and Delta in which flows a conserved current. The equivalence is established via the theorem of minimum energy dissipation within circuits having these structures.

Vector solitons in a spin-orbit-coupled spin-2 Bose-Einstein condensate

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

Elucidating the real-time Ag nanoparticle growth on alpha-Ag2WO4 during electron beam irradiation: experimental evidence and theoretical insights

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

Study of elastic properies of Ti3Al intermetallic compound using the ab initio calculation

The elastic properties of a Ti3Al intermetallic compound were studied using full potential (FP LAPW ) with the APW+lo method. The FP-LAPW is among the most accurate band structure calculations currently available and is based on the density functional theory with general gradient approximation for the exchange and correlation potential. This method provides the structural properties of the ground state as bulk modulus, equilibrium lattice parameter, and equilibrium minimum energy, and the elastic properties as shear modulus, young modulus, Zener coefficient (anisotropy), and Poisson coefficient. The calculated elastic properties are coherent with the elastic properties of the material.

Distorções harmônicas produzidas por inversores de geração distribuída fotovoltaica em condição de ressonância paralela

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Dados espectroscópicos de diterpenos labdânicos: uma análise teórica via RMN e DFT

Labdane diterpenes exhibit important bioactivities such as cardiovascular effects in rats as well as effects in the treatment of autoimmune diseases and Alzheimer syndrome. Recently, the labdane diterpenes ent-13-epi-manoil oxide, ribenone and ribenol were isolated from Croton palanostigma. The computational method DFT/B3LYP/cc-pVDZ was used to optimize the structures of these diterpenes and to calculate infrared data. Chemical shifts (δ_H and δ_C) of the minimum energy structures (local minimum) were calculated and compared with the experimental data. Comparison of the NMR data by simple linear regression (SLR) showed satisfactory statistical results with a correlation coefficient (R²) and predictive ability (Q²) of over 98%. The predicted NMR data were used to confirm the δ_H values that have not been published.

Theoretical study of the absorption and nonradiative deactivation of 1-nitronaphthalene in the low-lying singlet and triplet excited states including methanol and ethanol solvent effects

The photophysics of the 1-nitronaphthalene molecular system, after the absorption transition to the first singlet excited state, is theoretically studied for investigating the ultrafast multiplicity change to the triplet manifold. The consecutive transient absorption spectra experimentally observed in this molecular system are also studied. To identify the electronic states involved in the nonradiative decay, the minimum energy path of the first singlet excited state is obtained using the complete active space self-consistent field//configurational second-order perturbation approach. A near degeneracy region was found between the first singlet and the second triplet excited states with large spin-orbit coupling between them. The intersystem crossing rate was also evaluated. To support the proposed deactivation model the transient absorption spectra observed in the experiments were also considered. For this, computer simulations using sequential quantum mechanic-molecular mechanic methodology was used to consider the solvent effect in the ground and excited states for proper comparison with the experimental results. The absorption transitions from the second triplet excited state in the relaxed geometry permit to describe the transient absorption band experimentally observed around 200 fs after the absorption transition. This indicates that the T-2 electronic state is populated through the intersystem crossing presented here. The two transient absorption bands experimentally observed between 2 and 45 ps after the absorption transition are described here as the T-1 -> T-3 and T-1 -> T-5 transitions, supporting that the intermediate triplet state (T-2) decays by internal conversion to T-1. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4738757]

Trans-Planckian problem in the healthy extension of Horava-Lifshitz gravity

Planck scale physics may influence the evolution of cosmological fluctuations in the early stages of cosmological evolution. Because of the quasiexponential redshifting, which occurs during an inflationary period, the physical wavelengths of comoving scales that correspond to the present large-scale structure of the Universe were smaller than the Planck length in the early stages of the inflationary period. This trans-Planckian effect was studied before using toy models. The Horava-Lifshitz (HL) theory offers the chance to study this problem in a candidate UV complete theory of gravity. In this paper we study the evolution of cosmological perturbations according to HL gravity assuming that matter gives rise to an inflationary background. As is usually done in inflationary cosmology, we assume that the fluctuations originate in their minimum energy state. In the trans-Planckian region the fluctuations obey a nonlinear dispersion relation of Corley-Jacobson type. In the "healthy extension" of HL gravity there is an extra degree of freedom which plays an important role in the UV region but decouples in the IR, and which influences the cosmological perturbations. We find that in spite of these important changes compared to the usual description, the overall scale invariance of the power spectrum of cosmological perturbations is recovered. However, we obtain oscillations in the spectrum as a function of wave number with a relative amplitude of order unity and with an effective frequency which scales nonlinearly with wave number. Taking the usual inflationary parameters we find that the frequency of the oscillations is so large as to render the effect difficult to observe.

Structures of Cage, Prism, and Book Isomers of Water Hexamer from Broadband Rotational Spectroscopy

Theory predicts the water hexamer to be the smallest water cluster with a three-dimensional hydrogen-bonding network as its minimum energy structure. There are several possible low-energy isomers, and calculations with different methods and basis sets assign them different relative stabilities. Previous experimental work has provided evidence for the cage, book, and cyclic isomers, but no experiment has identified multiple coexisting structures. Here, we report that broadband rotational spectroscopy in a pulsed supersonic expansion unambiguously identifies all three isomers; we determined their oxygen framework structures by means of oxygen-18–substituted water (H218O). Relative isomer populations at different expansion conditions establish that the cage isomer is the minimum energy structure. Rotational spectra consistent with predicted heptamer and nonamer structures have also been identified.

Structures, energetics and fragmentation pathways of CnH22+ carbodications

Potential energy curves have been calculated for CnH22+ (n = 2−9) ions and results have been compared with data on unimolecular charge-separation reactions obtained by Rabrenović and Beynon. Geometry-optimized, minimum energy, linear CnH22+ structures have been computed for ground and low-lying excited states. These carbodications exist in stable configurations with well depths greater than 3 eV. Decomposition pathways into singly charged fragment ions lead to products with computed kinetic energies in excess of 1 eV. A high degree of correlation exists between experimental information and results computed for linear CnH22+ structures having hydrogen atoms on each end. The exception involves C4H22+reactions where a low-lying doubly charged isomer must be invoked to rationalize the experimental data.

C-3 Alkyl /Arylalkyl-2,3-dideoxy hex-2-enopyranosides as Antitubercular Agents: Synthesis, Biological Evaluation and QSAR Study

A series of C-3 alkyl and arylalky 2,3-dideoxy hex-2-enopyranoside derivatives were synthesized by Morita-Baylis-Hillman reaction using enulosides 4, 5 and 6 and various aliphatic and aromatic aldehydes. The compounds were evaluated in vitro for the complete inhibition of growth of Mycobacterium tuberculosis H37Rv. They exhibited moderate to good activity in the range of 25-1.56 µg/mL. Among these, 4d, 4h, 5c and 4hr showed activity at minimum inhibitory concentrations, 3.12, 6.25, 1.56 and 1.56µg/mL, respectively. These compounds were safe against cytotoxicity in VERO cell line and mouse macrophage cell line J 744A.1. A QSAR analysis by CP-MLR with alignment-free 3D-descriptors indicated the relevance of structure space comparable to the minimum energy conformation (from conformational analysis) of 5c to the activity. The study indicates that the compounds attaining conformational space 5c and reflecting some symmetry, minimum eccentricity and closely placed geometric and electronegativity centers therein are favorable for activity.

Experimental and Calculated Spectra of π-Stacked Mild Charge-Transfer Complexes: Jet-Cooled Perylene·(Tetrachloroethene) n , n = 1,2

The S0 ↔ S1 spectra of the mild charge-transfer (CT) complexes perylene·tetrachloroethene (P·4ClE) and perylene·(tetrachloroethene)2 (P·(4ClE)2) are investigated by two-color resonant two-photon ionization (2C-R2PI) and dispersed fluorescence spectroscopy in supersonic jets. The S0 → S1 vibrationless transitions of P·4ClE and P·(4ClE)2 are shifted by δν = −451 and −858 cm–1 relative to perylene, translating to excited-state dissociation energy increases of 5.4 and 10.3 kJ/mol, respectively. The red shift is ∼30% larger than that of perylene·trans-1,2-dichloroethene; therefore, the increase in chlorination increases the excited-state stabilization and CT character of the interaction, but the electronic excitation remains largely confined to the perylene moiety. The 2C-R2PI and fluorescence spectra of P·4ClE exhibit strong progressions in the perylene intramolecular twist (1au) vibration (42 cm–1 in S0 and 55 cm–1 in S1), signaling that perylene deforms along its twist coordinate upon electronic excitation. The intermolecular stretching (Tz) and internal rotation (Rc) vibrations are weak; therefore, the P·4ClE intermolecular potential energy surface (IPES) changes little during the S0 ↔ S1 transition. The minimum-energy structures and inter- and intramolecular vibrational frequencies of P·4ClE and P·(4ClE)2 are calculated with the dispersion-corrected density functional theory (DFT) methods B97-D3, ωB97X-D, M06, and M06-2X and the spin-consistent-scaled (SCS) variant of the approximate second-order coupled-cluster method, SCS-CC2. All methods predict the global minima to be π-stacked centered coplanar structures with the long axis of tetrachloroethene rotated by τ ≈ 60° relative to the perylene long axis. The calculated binding energies are in the range of −D0 = 28–35 kJ/mol. A second minimum is predicted with τ ≈ 25°, with ∼1 kJ/mol smaller binding energy. Although both monomers are achiral, both the P·4ClE and P·(4ClE)2 complexes are chiral. The best agreement for adiabatic excitation energies and vibrational frequencies is observed for the ωB97X-D and M06-2X DFT methods.

Modeling the Histidine–Phenylalanine Interaction: The NH···π Hydrogen Bond of Imidazole·Benzene

NH···π hydrogen bonds occur frequently between the amino acid side groups in proteins and peptides. Data-mining studies of protein crystals find that ~80% of the T-shaped histidine···aromatic contacts are CH···π, and only ~20% are NH···π interactions. We investigated the infrared (IR) and ultraviolet (UV) spectra of the supersonic-jet-cooled imidazole·benzene (Im·Bz) complex as a model for the NH···π interaction between histidine and phenylalanine. Ground- and excited-state dispersion-corrected density functional calculations and correlated methods (SCS-MP2 and SCS-CC2) predict that Im·Bz has a Cs-symmetric T-shaped minimum-energy structure with an NH···π hydrogen bond to the Bz ring; the NH bond is tilted 12° away from the Bz C₆ axis. IR depletion spectra support the T-shaped geometry: The NH stretch vibrational fundamental is red shifted by −73 cm⁻¹ relative to that of bare imidazole at 3518 cm⁻¹, indicating a moderately strong NH···π interaction. While the Sₒ(A1g) → S₁(B₂u) origin of benzene at 38 086 cm⁻¹ is forbidden in the gas phase, Im·Bz exhibits a moderately intense Sₒ → S₁ origin, which appears via the D₆h → Cs symmetry lowering of Bz by its interaction with imidazole. The NH···π ground-state hydrogen bond is strong, De=22.7 kJ/mol (1899 cm⁻¹). The combination of gas-phase UV and IR spectra confirms the theoretical predictions that the optimum Im·Bz geometry is T shaped and NH···π hydrogen bonded. We find no experimental evidence for a CH···π hydrogen-bonded ground-state isomer of Im·Bz. The optimum NH···π geometry of the Im·Bz complex is very different from the majority of the histidine·aromatic contact geometries found in protein database analyses, implying that the CH···π contacts observed in these searches do not arise from favorable binding interactions but merely from protein side-chain folding and crystal-packing constraints. The UV and IR spectra of the imidazole·(benzene)₂ cluster are observed via fragmentation into the Im·Bz+ mass channel. The spectra of Im·Bz and Im·Bz₂ are cleanly separable by IR hole burning. The UV spectrum of Im·Bz₂ exhibits two 000 bands corresponding to the Sₒ → S₁ excitations of the two inequivalent benzenes, which are symmetrically shifted by −86/+88 cm⁻¹ relative to the 000 band of benzene.

Emissions Control and the Regulation of Product Markets: The Case of Automobiles

The paper investigates alternative policies to regulate emissions from polluting product markets, specifically considering the case of the automobiles market. The two policies we consider are: a quota that limits the quantity produced of the polluting model and a more flexible average efficiency standard that requires a minimum energy efficiency across all models produced by a firm, similar to the US Corporate Average Fuel Economy (CAFE) standards. We use a duopoly model of vertical differentiation where firms produce both an economy (i.e., low polluting) version and a luxury (i.e., high polluting) version of a given product. We show that while a quota can raise firm profit over a certain range, CAFE always reduces firm profit relative to the pre-regulation. We also show that while the quota reduces emissions, it is possible that emissions increase under CAFE. The optimal policy choice will depend on the magnitude of unit damages. We show that when unit damages are sufficiently high, the quota policy is more efficient than the average efficiency standard. This suggests that instead of tightening CAFE to limit damages from emissions, policy makers can shift to a quota policy which is both welfare enhancing and more profitable for firms.