Saturation capability of short phase modulated pulses facilitates the measurement of longitudinal relaxation times of quadrupolar nuclei

The ability of various pulse types, which are commonly applied for distance measurements, to saturate or invert quadrupolar spin polarization has been compared by observing their effect on magnetization recovery curves under magic-angle spinning. A selective central transition inversion pulse yields a bi-exponential recovery for a diamagnetic sample with a spin-3/2, consistent with the existence of two processes: the fluctuations of the electric field gradients with identical single (W₁) and double (W₂) quantum quadrupolar-driven relaxation rates, and spin exchange between the central transition of one spin and satellite transitions of a dipolar-coupled similar spin. Using a phase modulated pulse, developed for distance measurements in quadrupolar spins (Nimerovsky et al., JMR 244, 2014, 107-113) and suggested for achieving the complete saturation of all quadrupolar spin energy levels, a mono-exponential relaxation model fits the data, compatible with elimination of the spin exchange processes. Other pulses such as an adiabatic pulse lasting one-third of a rotor period, and a two-rotor-period long continuous-wave pulse, both used for distance measurements under special experimental conditions, yield good fits to bi-exponential functions with varying coefficients and time constants due to variations in initial conditions. Those values are a measure of the extent of saturation obtained from these pulses. An empirical fit of the recovery curves to a stretched exponential function can provide general recovery times. A stretching parameter very close to unity, as obtained for a phase modulated pulse but not for other cases, suggests that in this case recovery times and longitudinal relaxation times are similar. The results are experimentally demonstrated for compounds containing ¹¹B (spin-3/2) and ⁵¹V (spin-7/2). We propose that accurate spin lattice relaxation rates can be measured by a short phase modulated pulse (<1-2ms), similarly to the "true T₁" measured by saturation with an asynchronous pulse train (Yesinowski, JMR 252, 2015, 135-144).