0000000000328592
AUTHOR
I. Chang
Translational and rotational molecular motion in supercooled liquids studied by NMR and forced Rayleigh scattering
It has been shown that translational diffusion coefficients, Dt, in the supercooled van der Waals liquids, orthoterphenyl, phenolphthaleindimethylether, and salol, have a weaker temperature dependence than the shear viscosity, η, at T ≲ 1.2Tg and can be described by Dt ∼ η−χ with χ < 1 whereas Dr ∼ η−1 applies for the mean rotational diffusion coefficients, Dr, down to the glass transition temperature, Tg. This apparent decoupling of translational and rotational motion has been discussed in relation with possible anomalous short time diffusion, spatial heterogeneity, and cooperative molecular motions close to Tg.
Self-diffusion coefficients in plastic crystals by multiple-pulse NMR in large static field gradients.
Measurements of self-diffusion coefficients in solids with the gradient spin echo technique have until now been limited due to short spin-spin relaxation times. Here we make use of multiple-pulse sequences, which average out the nuclear dipole interaction, to expand the measurable range for macroscopic self-diffusion coefficients by 2 orders of magnitude. By combining multiple-pulse NMR, in our case using the MREV-8 sequence, with a high static gradient we measured the self-diffusion coefficient in a molecular crystal of camphene down to a value of $D\phantom{\rule{0ex}{0ex}}=\phantom{\rule{0ex}{0ex}}3\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}16}{\mathrm{m}}^{2}{\mathrm{s}}^{\en…
Far-off-resonance averaging of dipolar interactions in solids
Abstract The far-off-resonance performance of several line-narrowing sequences is investigated. Both theoretically and experimentally, it is found that transverse relaxation times, dominated by dipole–dipole interactions, are most effectively prolonged not only on-resonance but also for certain, generally large, resonance offsets. These correspond to a situation when, during the basic pulse separation, the frequency offset rotates the toggling-frame Hamiltonian by multiples of 180°. The implications of these results for the study of macroscopic translational diffusion using static-field-gradient NMR are discussed.
Mössbauer investigations on glass-forming organic liquids
Glycerol forms a molecular glass near 180K. Fe2+ dissolved in glycerol allows the study of the dynamics of the system by Mossbauer spectroscopy. Recently it has been shown that the Mossbauer spectra can be understood in a way consistent with the results of dielectric and ultrasonic viscoelastic relaxation measurements. A jump diffusion model of Sinqwi and Sjolander with a jump rate distribution according to Davidson and Cole allowed us to fit the Mossbauer spectra of Fe in glycerol. First attempts to compare mode coupling theory with Mossbauer spectra are reported.
Dielectric relaxation models applied of the dynamics of myoglobin as determined by Mössbauer spectroscopy
Abstract Protein specific modes of motions are found in myoglobin crystals above 180 K. In this contribution we show that this type of motions can be analyzed by a Davidson-Cole, a Cole-Cole or a Havriliak-Negami distribution in analogy to dielectric relaxation. However, the temperature dependence of the obtained parameters is quite unusual indicating a broadening of the distributions with temperature instead of motional narrowing. This can be understood from the picture of conformational substates if one assumes that more and more substates become accessible with increasing temperature. The result shows that the analogy between glass forming organic liquids and proteins should not be exagg…