973 resultados para Vibrational circular dichroism


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Vibrational density of states (VDOS) in a supercooled polydisperse liquid is computed by diagonalizing the Hessian matrix evaluated at the potential energy minima for systems with different values of polydispersity. An increase in polydispersity leads to an increase in the relative population of localized high-frequency modes. At low frequencies, the density of states shows an excess compared to the Debye squared-frequency law, which has been identified with the boson peak. The height of the boson peak increases with polydispersity and shows a rather narrow sensitivity to changes in temperature. While the modes comprising the boson peak appear to be largely delocalized, there is a sharp drop in the participation ratio of the modes that exist just below the boson peak indicative of the quasilocalized nature of the low-frequency vibrations. Study of the difference spectrum at two different polydispersity reveals that the increase in the height of boson peak is due to a population shift from modes with frequencies above the maximum in the VDOS to that below the maximum, indicating an increase in the fraction of the unstable modes in the system. The latter is further supported by the facilitation of the observed dynamics by polydispersity. Since the strength of the liquid increases with polydispersity, the present result provides an evidence that the intensity of boson peak correlates positively with the strength of the liquid, as observed earlier in many experimental systems.

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The problem is solved using the Love function and Flügge shell theory. Numerical work has been done with a computer for various values of shell geometry parameters and elastic constants.

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When a fluid with memory is injected into any flow region some assumptions regarding the initial state of stress have to be made in order to determine the state of stress at any subsequent instant. For a Maxwell fluid, it is assumed that the fluid near the surface of injection is suddenly stressed and responds by starting flow in accordance with the mechanical model chosen. The flow of a Maxwell fluid with a single relaxation time has been determined under the above assumption in the following two cases: (i) annulus between two porous concentric circular cylinders, and (ii) space between two porous and infinitely extending parallel plates. The nature of flow in the present case is similar to that of the Reiner-Rivlin fluids obtained by Narasimhan2).

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A few red degraded bands attributable to NS have been reported earlier by Fowler and Barker, Dressler and Barrow et al, and they occur in the same region (2300 to 2700 Å) as the bands of the known systems (C2∑+-X2P{cyrillic}) and (A2Δ-X2P{cyrillic}). Measurements made on the heads of some of these weak bands led Barrow et al. to believe that these bands may form a system analogous to the β-system of NO and be due to a2P{cyrillic}-2P{cyrillic} transition. The spectrum of NS has now been studied in a little more detail by means of an uncondensed discharge through dry nitrogen and sulphur vapour in the presence of argon and thirty three bands belonging to this system have been recorded in the region 2280 to 2760 Å. It has been found possible to represent the band heads by means of the equation {Mathematical expression}. Taking the lower state doublet interval as 223 cm-1, it is shown that the separation in the upper state is 94 cm-1. The ratio of the force constants in the upper and the ground states is found to be 0·39 and is nearly the same as that in the β-system of NO (0·30). The present vibrational analysis therefore supports the view that these new red degraded bands of NS arise from a (B2P{cyrillic}→X2P{cyrillic}) transition and the observed intensity distribution in the form of a wide parabola is also in qualitative agreement with what is expected from the moderately large Δ re (∼0·12Å) value.

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A detailed study of various reversed phase systems for the qualitative analysis of fatty acids has been made and it has been shown, among other things, that the liquid paraffin-aqueous methanol system is a most convenient one. The details of a fairly simple and rapid method for the quantitative estimation of higher fatty acids have also been discussed.

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A comparatively simple and rapid method for the identification, estimation and preparation of fatty acids has been developed, using reversed phase circular paper chromatography. The method is also suitable for the analysis of “Critical Pairs” of fatty acids and for the preparation of fatty acids. Further, when used at a higher temperature, the method is more sensitive in revealing the presence of even traces of higher fatty acids in the seeds of Adenanthera pavonina.

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A finite circular cylindrical shell subjected to a band of uniform pressure on its outer rim was investigated, using three-dimensional elasticity theory and the classical shell theories of Timoshenko (or Donnell) and Flügge. Detailed comparison of the resulting stresses and displacements was carried out for shells with ratios of inner to outer shell radii equal to 0.80, 0.85, 0.90 and 0.93 and for ratios of outer shell diameter to length of the shell equal to 0.5, 1 and 2. The ratio of band width to length of the shell was 0.2 and Poisson's ratio used was equal to 0.3. An Elliot 803 digital computer was used for numerical computations.

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The force constants of H2 and Li2 are evaluated employing their extended Hartree-Fock wavefunctions by a polynomial fit of their force curves. It is suggested that, based on incomplete multiconfiguration Hartree-Fock wavefunctions, force constants calculated from the energy derivatives are numerically more accurate than those obtained from the derivatives of the Hellmann-Feynman forces. It is observed that electrons relax during the nuclear vibrations in such a fashion as to facilitate the nuclear motions.