Hyperfine effects in the nuclear magnetic resonance of paramagnetic molecules

Paramagnetic, or open-shell, systems are often encountered in the context of metalloproteins, and they are also an essential part of molecular magnets. Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for chemical structure elucidation, but for paramagnetic molecules it is substantially more complicated than in the diamagnetic case. Before the present work, the theory of NMR of paramagnetic molecules was limited to spin-1/2 systems and it did not include relativistic corrections to the hyperfine effects. It also was not systematically expandable. --- The theory was first expanded by including hyperfine contributions up to the fourth power in the fine structure constant α. It was then reformulated and its scope widened to allow any spin state in any spatial symmetry. This involved including zero-field splitting effects. In both stages the theory was implemented into a separate analysis program. The different levels of theory were tested by demonstrative density functional calculations on molecules selected to showcase the relative strength of new NMR shielding terms. The theory was also tested in a joint experimental and computational effort to confirm assignment of 11 B signals. The new terms were found to be significant and comparable with the terms in the earlier levels of theory. The leading-order magnetic-field dependence of shielding in paramagnetic systems was formulated. The theory is now systematically expandable, allowing for higher-order field dependence and relativistic contributions. The prevailing experimental view of pseudocontact shift was found to be significantly incomplete, as it only includes specific geometric dependence, which is not present in most of the new terms introduced here. The computational uncertainty in density functional calculations of the Fermi contact hyperfine constant and zero-field splitting tensor sets a limit for quantitative prediction of paramagnetic shielding for now.

Experimental investigation of three-layer electromagnetically coupled circular microstrip antennas

The broadband behaviour of a three-layer electromagnetically coupled circular microstrip antenna is investigated experimentally. The effects of interlayer spacings and the thickness of the parasitic layers on the impedance bandwidth, 3 dB beamwidth and pattern shape, are studied. Experiments show that this structure can provide a frequency bandwidth as high as 20% with a low crosspolarisation level and a moderately high gain.

Flow And Heat-Transfer Over An Upstream Moving Wall With A Magnetic-Field And A Parallel Free Stream

The flow and heat transfer over an upstream moving non-isothermal wall with a parallel free stream have been considered. The magnetic field has been applied in the free stream parallel to the wall and the effect of induced magnetic field has been included in the analysis. The boundary layer equations governing the steady incompressible electrically conducting fluid flow have been solved numerically using a shooting method. This problem is interesting because a solution exists only when the ratio of the wall velocity does not exceed a certain critical value and this critical value depends on the magnetic field and magnetic Prandtl number. Also dual solutions exist for a certain range of wall velocity.

Geometrically simple linear weirs using circular quadrants

A detailed theoretical analysis of flow through a quadrant plate weir is made in the light of the generalized theory of proportional weirs, using a numerical optimization procedure. It is shown that the flow through the quadrant plate weir has a linear discharge-head relationship valid for certain ranges of head. It is shown that the weir is associated with a reference plane or datum from which all heads are reckoned.Further, it is shown that the measuring range of the quadrant plate weir can be considerably enhanced by extending the tangents to the quadrants at the terminals of the quadrant plate weir. The importance of this weir (when the datum of the weir lies below its crest) as an outlet weir for grit chambers is highlighted. Experiments show excellent agreement with the theory by giving a constant average coefficient of discharge.