Sample convection in liquid-state NMR: Why it is always with us, and what we can do about it

AbstractMany NMR experiments on liquids suffer if the sample convects. This is particularly true for applications, such as the measurement of diffusion, that rely on spatial labelling of spins. It is widely assumed that, in most well-conducted experiments with stable temperature regulation, samples do not convect. Unfortunately this is not the case. It is shown here that typical NMR samples show measurable convective flow for all but a very narrow range of temperatures; convection is seen both above and below this range, which can be as small as a degree or so for a mobile solvent such as chloroform. This convection is driven by both vertical and horizontal temperature gradients.Measurements of convection velocity are presented for a range of samples, sample tubes, probes, and temperatures. Both decreasing sample tube inner diameter and changing sample tube material from glass to sapphire can slow convection markedly, with sapphire tubes being particularly effective. Such tubes are likely to be particularly helpful for accurate measurement of diffusion by NMR

Orbiting Resonances and Bound States in Molecular Scattering

A family of orbiting resonances in molecular scattering is globally described by using a single pole moving in the complex angular momentum plane. The extrapolation of this pole at negative energies gives the location of the bound states. Then a single pole trajectory, that connects a rotational band of bound states and orbiting resonances, is obtained. These complex angular momentum singularities are derived through a geometrical theory of the orbiting. The downward crossing of the phase-shifts through pi/2, due to the repulsive region of the molecular potential, is estimated by using a simple hard-core model. Some remarks about the difference between diffracted rays and orbiting are also given.Comment: 18 pages, 3 figures, to appear in Physical Review