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Bonifac Legrady

Publications and source records attributed to Bonifac Legrady.

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Spinor Double-Quantum Excitation in the Solution NMR of Near-Equivalent Spin-1/2 Pairs

A family of double-quantum excitation schemes is described for the solution nuclear magnetic resonance (NMR) of near-equivalent spin-1/2 pairs. These new methods exploit the spinor behaviour of 2-level systems, whose signature is the change of sign of a quantum state upon a $2π$ rotation. The spinor behaviour is used to manipulate the phases of single-quantum coherences, in order to prepare a double-quantum precursor state which is rapidly converted into double-quantum coherence by a straightforward $π/2$ rotation. One set of spinor-based methods exploits symmetry-based pulse sequences, while the other set exploits SLIC (spin-lock-induced crossing), in which the nutation frequency under a resonant radiofrequency field is matched to the spin-spin coupling. A variant of SLIC is introduced which is well-compensated for deviations in the radiofrequency field amplitude. The methods are demonstrated by performing double-quantum-filtered $^{19}$F NMR on a molecular system containing a pair of diastereotopic $^{19}$F nuclei. The new methods are compared with existing techniques.

quant-ph

The $^{103}$Rh NMR Spectroscopy and Relaxometry of the Rhodium Formate Paddlewheel Complex

The NMR spectroscopy of spin-1/2 nuclei with low gyromagnetic ratio is challenging, due to the low NMR signal strength. Methodology for the rapid acquisition of $^{103}$Rh NMR parameters is demonstrated for the case of the rhodium formate "paddlewheel" complex $\mathrm{Rh_2(HCO_2)_4}$. A scheme is described for enhancing the $^{103}$Rh signal strength by polarization transfer from $^{1}$H nuclei and which also greatly reduces the interference from ringing artifacts, a common hurdle for the direct observation of low-$γ$ nuclei. The $^{103}$Rh relaxation time constants $T_1$ and $T_2$ are measured within 20 minutes using $^{1}$H-detected experiments. The field-dependence of the $^{103}$Rh $T_1$ is measured. The high-field relaxation is dominated by the chemical shift anisotropy (CSA) mechanism. The $^{103}$Rh shielding anisotropy is found to be very large: $|Δσ|=9900\pm540\mathrm{\,ppm}$. This estimate is compared with density functional theory calculations.

physics.chem-ph