Solid state molecular motions

For these reasons, PMMA and its maleimide and glutarimide copolymers represent very suitable materials for investigating the effect of the chemical structure and of the solid state molecular motions on the plastic deformation, the occurrence of the various micro-mechanisms of deformation (chain scission crazes, shear deformation zones, chain disentanglement crazes), as well as the fracture behaviour. 

G. B. Buchanan, G. McManus, and H. C. Jarell, Solid state molecular motion in sucrose octapalmitate as studied by deuterium NMR spectroscopy, Chem. Phys. Lipids, 104 (2000) 23-34. 

Yannoni CS, Johnson RD, Meijer G, Bethune DS, Salem JR (1991) Carbon-13 NMR study of the C60 cluster in the solid state molecular motion and carbon chemical shift anisotropy. J Phys Chem 95 9... 

D. S. Bethune and J. R. Salem, C NMR Study of the Ceo Cluster in the Solid State Molecular Motion and Carbon Chemical Shift Anisotropy, J. Phys. Chem. 95,9-10 (1991). 

The main uses of NQR are (i) information about chemical bonding in the solid state (ii) molecular structure information (Hi) characterisation of molecular or ionic species (fingerprinting) (iv) crystallographic and molecular symmetry information (v) solid-state molecular motion studies (vi) phase transitions and (vii) studies of impurities. The reason for the relatively limited practical application of NQR seems to lie in the scarcity of sufficiently sophisticated equipment. 

Uehara H, Yamanobe T, Komoto T. Relationship between solid-state molecular motion and morphology for ultrahigh molecular weight polyethylene crystallized under different conditions. Macromolecules 2000 33 4861. 

The principal dilTerence from liquid-state NMR is that the interactions which are averaged by molecular motion on the NMR timescale in liquids lead, because of their anisotropic nature, to much wider lines in solids. Extra infonnation is, in principle, available but is often masked by the lower resolution. Thus, many of the teclmiques developed for liquid-state NMR are not currently feasible in the solid state. Furthemiore, the increased linewidth and the methods used to achieve high resolution put more demands on the spectrometer. Nevertheless, the field of solid-state NMR is advancing rapidly, with a steady stream of new experiments forthcoming. 

Models for description of liquids should provide us with an understanding of the dynamic behavior of the molecules, and thus of the routes of chemical reactions in the liquids. While it is often relatively easy to describe the molecular structure and dynamics of the gaseous or the solid state, this is not true for the liquid state. Molecules in liquids can perform vibrations, rotations, and translations. A successful model often used for the description of molecular rotational processes in liquids is the rotational diffusion model, in which it is assumed that the molecules rotate by small angular steps about the molecular rotation axes. One quantity to describe the rotational speed of molecules is the reorientational correlation time T, which is a measure for the average time elapsed when a molecule has rotated through an angle of the order of 1 radian, or approximately 60°. It is indirectly proportional to the velocity of rotational motion. 

With concern to the high internal mobility of the molecules in the high temperature solid state phase, some parallelism to n-alkanes can be stated. In the pseudohexagonal (rotator) phase the latter are also characterized by fast molecular motions. For discrimination and according to Pfitzer 14) and Dale 13) in the following the term pseudorotator phase is used for the mobil crystalline state of cyclic molecules. 

There is a second relaxation process, called spin-spin (or transverse) relaxation, at a rate controlled by the spin-spin relaxation time T2. It governs the evolution of the xy magnetisation toward its equilibrium value, which is zero. In the fluid state with fast motion and extreme narrowing 7) and T2 are equal in the solid state with slow motion and full line broadening T2 becomes much shorter than 7). The so-called 180° pulse which inverts the spin population present immediately prior to the pulse is important for the accurate determination of T and the true T2 value. The spin-spin relaxation time calculated from the experimental line widths is called T2 the ideal NMR line shape is Lorentzian and its FWHH is controlled by T2. Unlike chemical shifts and spin-spin coupling constants, relaxation times are not directly related to molecular structure, but depend on molecular mobility. 

The analogy drawn between -stacked solids and duplex DNA has provided a useful starting point for experiments to probe and understand DNA-medi-ated CT. As with the -stacked solids, the DNA base pair array can provide an effective medium for long range CT. Mechanistically, however, the differences between DNA and these solid state materials may be even more important to consider. Duplex DNA, as a molecular -stacked structure, undergoes dynamical motion in solution. The time-dependent and sequence-dependent structures that arise serve to modulate and gate CT. Indeed in probing DNA CT as a function of sequence and sequence-dependent structure, we may better understand mechanistically how CT proceeds and how DNA CT may be utilized. 

The polymer at the gel point is in a critical state [3], and the name critical gel [4] is appropriate for distinguishing polymers at the gel point from the various materials which commonly are called gels. The critical gel has no intrinsic size scale except for the size of its oligomeric building block, and molecular motions are correlated over large distances. The combination of liquid and solid... 

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