Raman and IR Spectroscopy of a Mixed CH3CN-H2O Solvent in the Cn Stretching Region

Raman and IR spectroscopy have been used to elucidate the solvation process in a mixed water-acetonitrile solvent in the CN stretching region. The number and positions of the components forming the spectral contour are established by Fourier deconvolution and Factor analysis and their areas are determined by fitting. The forms of existence of acetonitrile in the mixed solvent are discussed.     

Rapid crack growth in a thermoelastic solid under mixed-mode thermomechanical loading

A two-dimensional steady-sate analysis of semi-infinite brittlecrack growth at a constant subcritical rate in an unboundedfully-coupled thermoelastic solid under mixed-mode thermomechanicalloading is made. The loading consists of normal and shear tractionsand heat fluxes applied as point sources (line loads in theout-of-plane direction). A related problem is solved exactly in an integral transformspace, and robust asymptotic forms used to reduce the originalproblem to a set of integral equations. The equations are partiallycoupled and exhibit operators of both Cauchy and Abel types,yet can be solved analytically. The temperature change field at a distance from the moving crackedge is then constructed, and its dominant term is found tobe controlled by the imposed heat fluxes. The role of this termis, indeed, enhanced if the heat fluxes serve to render thecrack as a net heat source/sink for the solid, as opposed tobeing a transmitter of heat across its plane. More generally,the influence of the thermoelastic coupling on this field, aswell as other functions, is found to increase with crack speed.     

Intermittency at critical transitions and aging dynamics at the onset of chaos

We recall that at both the intermittency transitions and the Feigenbaum attractor, in unimodal maps of non-linearity of order ζ > 1, the dynamics rigorously obeys the Tsallis statistics. We account for theq-indices and the generalized Lyapunov coefficients λ^q that characterize the universality classes of the pitchfork and tangent bifurcations. We identify the Mori singularities in the Lyapunov spectrum at the onset of chaos with the appearance of a special value for the entropic indexq. The physical area of the Tsallis statistics is further probed by considering the dynamics near criticality and glass formation in thermal systems. In both cases a close connection is made with states in unimodal maps with vanishing Lyapunov coefficients.     

Advantages of using a modified orthogonal sampling configuration originally designed for LC-ESI-MS to couple CE and MS for the determination of antioxidant phenolic compounds found in virgin olive oil

A ThermoFinnigan sheath liquid flow capillary electrophoresis-mass spectrometry system designed for coupling via a co-axial interface was coupled through an adapted via an alternative, commercially available interface for orthogonal sampling. The affordable, reversible structural alterations made in the commercial LC-MS interface resulted in improved analytical performance.The results of a conventional capillary electrophoresis (CE) method using a commercial co-axial source to determine antioxidant phenolic acids present in virgin olive oil, were compared with those obtained by using a modified orthogonal sampling position. In both cases, separations were done using a 10 mM ammonium acetate/ammonium hydroxide buffer solution at pH 10.0 and a constant applied voltage of 25 kV. The operating variables for the mass spectrometry interface were re-optimized for the modified orthogonal orientation. This allowed the sheath liquid, sheath gas flow rates and capillary voltage to be lowered with respect to the co-axial coupling configuration. In addition, the orthogonal sampling position provided a higher selectivity by effect of ion sampling excluding larger droplets—with an increased momentum along the axis—which were drained through the sink at the bottom of the ion source. Also, the new configuration facilitated sample ionization, improved electrospray stability and led to stronger signals as a result.The new system was validated in terms of precision (repeatability), linearity, and limits of detection and quantification. A comparison of the validation data with the results previously obtained by using a commercial co-axial configuration revealed the adapted orthogonal sampling position to provide better repeatability in both migration times and relative peak areas (<1% and 7% respectively with n = 15 replicates), a good linear range (with levels in the microgram-per-litre region) and lower limits of detection—especially for the compounds detected with the lowest sensitivity when co-axial ESI was used, as HFA, GEN, FER and VAN finding LOD among 24-3.0 μg L⁻¹ respectively.     

Chaos and unpredictability in evolutionary dynamics in discrete time

A discrete-time version of the replicator equation for two-strategy games is studied. The stationary properties differ from those of continuous time for sufficiently large values of the parameters, where periodic and chaotic behavior replace the usual fixed-point population solutions. We observe the familiar period-doubling and chaotic-band-splitting attractor cascades of unimodal maps but in some cases more elaborate variations appear due to bimodality. Also unphysical stationary solutions can have unusual physical implications, such as the uncertainty of the final population caused by sensitivity to initial conditions and fractality of attractor preimage manifolds.     

Microscopic theory of the isovector dipole resonance at high angular momenta

The giant dipole resonance at large angular velocities and finite temperatures is studied within the framwork of temperature-dependent linear response theory for superfluid Fermi liquids. The peak energy of the resonance and its splitting is discussed as a function of angular momentum and temperature. The influence of the shape and gap parameters on the fine structure is investigated.     

Linear attraction in quasi-linear difference systems

The equivalence and asymptotic equivalence between the solutions of a linear difference system and some families of quasi-linear ones are studied by using a Lipschitz component-wise condition combined with a spectrally small dichotomy, which is introduced. The equivalence is described by a homeomorphism and the results also include unbounded solutions. The results show the vectorial attractivity of the solutions of the linear part.