Ultrafast dynamics of aniline in the 294-234 nm excitation range: the role of the πσ∗ state

The ultrafast relaxation of jet-cooled aniline was followed by time-resolved ionization, after excitation in the 294-234 interval. The studied range of energy covers the absorption of the two bright ππ? excitations, S(1) and S(3), and the almost dark S(2) (πσ?) state. The employed probe wavelengths permit to identify different ultrafast time constants related with the coupling of the involved electronic surfaces. A τ(1) = 165 ± 30 fs lifetime is attributed to dynamics along the S(2) (πσ?) repulsive surface. Other relaxation channels as the S(1)→S(0) and S(3)→S(1) internal conversion are also identified and characterized. The work provides a general view of the photophysics of aniline, particularly regarding the role of the πσ? state. This state appears as minor dissipation process due to the ineffective coupling with the bright S(1) and S(3) states, being the S(1)→S(0) internal conversion the main non-radiative process in the full studied energy range. Additionally, the influence of the off-resonance adiabatic excitation of higher energy electronic states, particularly S(3), is also observed and discussed.     

Bonding and magnetic response properties of several toroid structures. Insights of the role of Ni2S2 as a building block from relativistic density functional theory calculations

Relativistic density functional calculations were carried out on several nickel toroid mercaptides of the general formula [Ni(μ-SR)(2)](n), with the aim to characterize and analyze their stability and magnetic response properties, in order to gain more insights into their stabilization and size-dependent behavior. The Ni-ligand interaction has been studied by means projected density of states and energy decomposition analysis, which denotes its stabilizing character. The graphical representation of the response to an external magnetic field is applied for the very first time taking into account the spin-orbit term. This map allows one to clearly characterize the magnetic behavior inside and in the closeness of the toroid structure showing the prescence of paratropic ring currents inside the Ni(n) ring, and by contrast, diatropic currents confined in each Ni(2)S(2) motif denoting an aromatic behavior (in terms of magnetic criteria). The calculated data suggests that the Ni(2)S(2) moiety can be regarded as a stable constructing block, which can afford several toroid structures of different nuclearities in agreement with that reported in the experimental literature. In addition, the effects of the relativistic treatment over the magnetic response properties on these lighter compounds are denoted by comparing nonrelativistic, scalar relativistic, and scalar plus spin-orbit relativistic treatments, showing their acting, although nonpronunced, role.     

Theory of spin transfer phenomena in magnetic metals and semiconductors

We propose a general theory of the spin-transfer effects that occur when current flows through inhomogeneous magnetic systems. Our theory does not rest on an appeal to conservation of total spin, can assess whether or not current-induced magnetization precession and switching in a particular geometry will occur coherently, and can estimate the efficacy of spin-transfer when spin-orbit interactions are present. We illustrate our theory by applying it to a toy-model twodimensional-electron-gas ferromagnet with Rashba spin-orbit interactions.     

Comparison of haemodynamics in cerebral aneurysms of different sizes located in the ophthalmic artery

Haemodynamics plays an important role in the progression and rupture of cerebral aneurysms. The temporal and spatial variations of the wall shear stress in the aneurysmal sac are hypothesized to be correlated with its growth and rupture. In addition, the assessment of the velocity field in the aneurysm dome and neck is important for the correct placement of endovascular coils. This work describes the flow dynamics in patient‐specific models of saccular aneurysms of different sizes located in the ophthalmic artery. The models were obtained from three‐dimensional rotational angiography image data and blood flow dynamics was studied under physiologically representative waveform of inflow. The three‐dimensional continuity and momentum equations for unsteady laminar flow were solved with commercial software using nonstructured fine grid sizes. The intra‐aneurysmal flows show complex vortex structures that change during one pulsatile cycle. A relation between the aneurysm aspect ratio and the mean wall shear stress on the aneurysmal sac is showed. Copyright © 2006 John Wiley & Sons, Ltd.     

Testing for cointegration using induced-order statistics

In this paper we explore the usefulness of induced-order statistics in the characterization of integrated series and of cointegration relationships. We propose a non-parametric test statistic for testing the null hypothesis of two independent random walks against wide cointegrating alternatives including monotonic nonlinearities and certain types of level shifts in the cointegration relationship. We call our testing device the induced-order Kolmogorov–Smirnov cointegration test (KS), since it is constructed from the induced-order statistics of the series, and we derive its limiting distribution. This non-parametric statistic endows the test with a number of desirable properties: invariance to monotonic transformations of the series, and robustness for the presence of important parameter shifts. By Monte Carlo simulations we analyze the small sample properties of this test. Our simulation results show the robustness of the induced order cointegration test against departures from linear and constant parameter models. This paper is an extension of the work of Aparicio and Granger (1995) and Aparicio and Escribano (1998).     

Far-infrared optical absorption due to surface phonon excitations in small metal particles

In this paper, the role played by the excitation of surface phonons in the far infrared optical absorption of small metallic spheres is explored. We find that for frequencies ranging between 100 cm^-3 and 200 cm^-1 this absorption mechanism is dominating over the ones coming from considering electronic excitations or the Joule heating.     

Synthesis of heterocyclic compounds IV1 pyrazol-1′-ylpyridines2

2-Pyrazol-1-ylpyridines were synthesized by condensation of pyridylhydrazines with 1,3-dicarbonyl compounds or by theUllmann arylation of pyrazoles with halopyridines.Taken in part from the Master's thesis ofA. A. A. Pinto, Instituto Militar de Engenharia, Rio de Janeiro, 1978.     

Efficient, accurate calculation of rotational diffusion and NMR relaxation of globular proteins from atomic-level structures and approximate hydrodynamic calculations

The calculation of the rotational diffusion tensor and NMR relaxation times of quasi-rigid macromolecular structures with atomic detail can be made by means of bead/shell models. The computing time required for calculation of these properties for a single structure using rigorous hydrodynamic methods requires a moderate computing time. In possible applications of the methodology in which such a calculation had to be repeated for many structures, a faster method would be welcome. We have studied the effect of introducing a simplifying approximation in the treatment of hydrodynamic interaction, comparing the rigorous and approximate results for a set of 30 globular proteins. When the NMR relaxation times are combined in some relative form, the rigorous and approximate results are practically coincident. For absolute quantities, such as the correlation time, we find that the bias introduced by the approximation can be closely predicted and corrected. The differences between the results of the approximate-corrected and rigorous procedures are not greater than usual experimental errors, and the typical computing time is reduced from 5 min to 1 s.