Liquid phase magnetic parameters

The most significant are the Zeeman (g tensor) and nitrogen hyperfine interactions. These depend somewhat on chemical structure, solvent polarity, and temperature. An assumption has been made almost universally that magnetic parameters that are found in frozen solutions may be used to describe liquid phase spectra. This assumption should be recognized and considered carefully in precise work. It may be invalid for several reasons, including (1) altered distribution of nitroxide molecular conformations,... 

It is sometimes possible to obtain rigid limit magnetic parameters from detailed analysis of liquid phase spectra. An example is the approach of Hyde and Rao [33]. 

The ordering of probe molecules in liquid crystals was in fact known much earlier than 1968. It is widely used to determine various parameters of the solute and solvent liquid crystal using nuclear magnetic resonance (NMR), electron spin resonance (ESR), ultraviolet (UV), visible, and other spectroscopie teehniques. After the pioneering work of Saupe and Englert in 1963 [8], the NMR spectroscopy of molecules oriented in liquid crystals became very important in structural chemistry, as it provides the only direct method for precise determination of the molecular geometries in liquid phase. In addition to structural and confor-... 

Since the first publications on this subject in 1963, NMR in liquid crystalline systems has been a wide and active field of research in many branches of organic and physical chemistry. In fact, NMR spectroscopy has revealed a powerful means of probing molecular structure, anisotropic magnetic parameters and dynamic behaviour of solute molecules dissolved in liquid crystals. Moreover, this technique has been successfully employed to investigate properties of mesophases themselves, such as their orientational ordering, translational and rotational diffusion and their effects on nuclear relaxation, and molecular organization in different liquid crystalline phases. 

For example, 0 describes the temperature dependence of composition near the upper critical solution temperature for binary (liquid + liquid) equilibrium, of the susceptibility in some magnetic phase transitions, and of the order parameter in (order + disorder) phase transitions. 

Not only do the thermodynamic properties follow similar power laws near the critical temperatures, but the exponents measured for a given property, such as heat capacity or the order parameter, are found to be the same within experimental error in a wide variety of substances. This can be seen in Table 13.3. It has been shown that the same set of exponents (a, (3, 7, v, etc.) are obtained for phase transitions that have the same spatial (d) and order parameter (n) dimensionalities. For example, (order + disorder) transitions, magnetic transitions with a single axis about which the magnetization orients, and the (liquid + gas) critical point have d= 3 and n — 1, and all have the same values for the critical exponents. Superconductors and the superfluid transition in 4He have d= 3 and n = 2, and they show different values for the set of exponents. Phase transitions are said to belong to different universality classes when their critical exponents belong to different sets. 

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