A robust Freeman-Hill-inspired pulse protocol for ringdown-free T₁ relaxation measurements

A new difference-spectroscopy method is introduced for measuring T₁ relaxation times. It is inspired by the earlier work of Freeman and Hill and eliminates the need for recording signal intensities at thermodynamic equilibrium. The new method is termed SIP-R (Split-Inversion Pulse and Recovery) and reduces the number of refinable parameters in the curve fitting process of relaxation-delay-dependent signal intensities by using two instead of the three parameters typically used in the standard inversion-recovery sequence. The SIP-R method preserves the dynamic range of measurement of the standard inversion-recovery method but converts the rise-to-maximum mathematical functionality of the recorded data into a decay-to-zero functionality. The decay-to-zero functionality renders the SIP-R sequence advantageous for inverse Laplace transformation numerical optimizations. The new technique proves to be extremely robust with respect to pulse imperfections, pulse-power changes during the pulse sequence, pulse-width miscalibrations, resonance offsets, and radiofrequency field variations. It also compensates for acoustic ring-down effects and proves reliable for measurements with inhomogeneously broadened signals up to several kilohertz linewidth. ¹H NMR experiments with methane gas at pressures up to 50 atm in toroid-cavity pressure vessel probes and in the presence of the methane-to-methanol conversion catalyst Cu-ZnO/Al₂O₃ are used to show the usefulness of the new method for relaxation time investigations under pressure, at strong radiofrequency field gradients, and in the presence of paramagnetic materials.