The Kirkwood correlation factor of dense methanol as a function of temperature and pressure under isochoric conditions and its statistical mechanical treatment

Experimental data of dielectric susceptibilities of methanol available in the literature over a wide range of temperature and pressure have been used for constructing a state function of the Kirkwood correlation factor g _K of methanol applicable in the homogeneous fluid region between 298 and 580?K and up to 350?MPa. Results of three isochores at 786.32, 820 and 850 kg m^?3 of this state function have been compared with predictions made by a statistical mechanical theory developed in previous work. The theory is based on an association model of alcohols accounting for the correlation of effective dipole moments of chains of all length as well as ringlike cluster formations. Most of the parameters such as association constants and association enthalpies have been obtained from quantum mechanical ab initio calculations of methanol clusters up to six members, reducing the numbers of adjustable parameters to three association constants and an averaged value of the angle between dipoles. The theory which has turned out to provide excellent results for alcohol + hydrocarbon and alcohol +?CCl₄ liquid mixtures at ambient pressure is also able to predict isochoric values of pure methanol up to a pressure of 350?MPa and temperatures of 570?K without adjusting further parameters in satisfying agreement with experimental data.     

A comparison of stochastic and effective medium approaches to the backscattered signal from a porous layer in a solid matrix

This paper reports a study of the backscattering behavior of a solid layer containing randomly spaced spherical cavities in the long wavelength limit. The motivation for the work arises from a need to model the responses of porous composite materials in ultrasonic NDE procedures. A comparison is made between models based on a summation over discrete scatterers, which show interesting emergent properties, and an integral formulation based on an ensemble average, and with a simple slab effective medium approximation. The similarities and differences between these three models are demonstrated. A simple quantitative criterion is established which sets the maximum frequency at which ensemble average or equivalent homogeneous medium models can represent echo signal generation in a porous layer for given interpore spacing, or equivalently, given pore size and concentration.     

Topological defects and cosmology

Many particle physics models of matter admit solutions corresponding to stable or long-lived topological defects. In the context of standard cosmology it is then unavoidable that such defects will form during phase transitions in the very early Universe. Certain types of defects lead to disastrous consequences for cosmology, others may play a useful role, as possible seeds for the formation of structure in the Universe, or in mediating baryon number violating processes. In all cases, topological defects lead to a fruitful interplay between particle physics and cosmology.     

The Contribution of Raman Scattering to the Fluorescence of the Polyene Antibiotic Amphotericin B

Fluorescence has recently been applied to the analysis of the molecular organization state of the polyene antibiotic amphotericin B (AmB) in solution or in lipid membranes. The polyene chain of AmB monomer gives rise to two fluorescence emissions; S₁(2¹A_g) → S₀(1¹A_g) between 500 and 700 nm, S₂(1¹B_u) → S₀(1¹A_g) between 400 and 500 nm. However, Raman scattering might interfere with the S₂ → S₀ emission fluorescence due to the weak fluorescence quantum yield and close proximity to the exciting lines. In fact, we show here that a change in the excitation wavelength results in a shift of three emission bands, an effect which excludes their assignment to fluorescence. These bands originate from the water Raman at 3382 cm^-1and AmB resonance Raman at 1556 and 1153 cm^-1. As a consequence, some former conclusions on the molecular organization state of AmB should be reconsidered.     

Solitons in geometric potentials

We show that the geometrically induced potential existing in undulated slab waveguides dramatically affects the properties of solitons. In particular, whereas solitons residing in the potential maxima do not feature power thresholds and are stable, their counterparts residing in the potential minima are unstable and may exhibit a power threshold for their existence. Additionally, the geometric potential is shown to support stable multipole solitons that cannot be supported by straight waveguides. Finally, the geometric potential results in the appearance of the effective barriers that prevent transverse soliton motion.     

Correcting reaction rates measured by saturation-transfer magnetic resonance spectroscopy

Off-resonance or spillover irradiation and incomplete saturation can introduce significant errors in the estimates of chemical rate constants measured by saturation-transfer magnetic resonance spectroscopy (MRS). Existing methods of correction are effective only over a limited parameter range. Here, a general approach of numerically solving the Bloch-McConnell equations to calculate exchange rates, relaxation times and concentrations for the saturation-transfer experiment is investigated, but found to require more measurements and higher signal-to-noise ratios than in vivo studies can practically afford. As an alternative, correction formulae for the reaction rate are provided which account for the expected parameter ranges and limited measurements available in vivo. The correction term is a quadratic function of experimental measurements. In computer simulations, the new formulae showed negligible bias and reduced the maximum error in the rate constants by about 3-fold compared to traditional formulae, and the error scatter by about 4-fold, over a wide range of parameters for conventional saturation transfer employing progressive saturation, and for the four-angle saturation-transfer method applied to the creatine kinase (CK) reaction in the human heart at 1.5 T. In normal in vivo spectra affected by spillover, the correction increases the mean calculated forward CK reaction rate by 6-16% over traditional and prior correction formulae.     

Internal magnetic fields in submicron particles of barium hexaferrite detected by 57Fe NMR

⁵⁷Fe nuclear magnetic resonance (NMR) spectra of hexaferrite BaFe₁₂O₁₉ powder samples prepared by glass crystallization method were measured at 4.2 K and analyzed in comparison to spectra of single crystals. Samples with various mean particle dimensions were tested. NMR spectral lines corresponding to individual iron sublattices showed pronounced frequency shifts of their positions and a significant line broadening compared to single crystals. The significant contribution to the line shifts and line shape had a uniform macroscopic origin giving identical absolute value of shifts and the same line shapes for all measured lines of a particular sample. Estimations of demagnetization fields based on mean particle dimensions reasonably corresponded to the observed frequency shifts for particle mean diameter 67 nm, or had a higher value for a sample with mean diameter of 340 nm, for which a presence of domain walls was detected by NMR. In the spectrum of a sample with the smallest particles (～16 nm), an additional contribution having broader lines and faster spin-spin relaxations was found. It could be assigned to weaker exchange interactions or deviations of magnetic moment directions from the hexagonal axis in a surface layer.     

Four complementary theoretical approaches for the analysis of NMR paramagnetic relaxation

Four theoretical and computational approaches used at the University of Michigan to analyze NMR paramagnetic relaxation enhancement (NMR-PRE) are described. The primary objective of the theory is to describe the relationship of the NMR-PRE phenomenon to the electron spin hamiltonian and the spin energy level structure when zero field splitting interactions are significant. Four formulations of theory are discussed: (1) spin dynamics simulation; (2) the laboratory frame "constant H(S)" formulation; (3) the Molecular Frame "constant H(S)" formulation; and (4) the zfs-limit "constant H(S)" formulation. No single theoretical approach describes all important aspects of the relaxation mechanism in a fully satisfactory way. We use the four formulations in a complementary manner to provide as complete a picture of the relaxation mechanism as possible. We also discuss the integration of NMR-PRE theory and recently developed theory of electron spin relaxation which accounts for effects of the permanent zfs hamiltonian.