A novel pulse scheme for multiple quantum excitation, SFAM to enhance the sensitivity of MQMAS experiments.

The basic MQMAS sequence consists of two hard pulses, one excites the equilibrium population to MQ (Multiple Quantum) coherence, and the other converts back to detectable coherence after some evolution time t1 (Medek et al., 1995). Unfortunately the MQ excitation and conversion processes are very inefficient due to the nonlinear nature of MQ processes. MQ conversion (converting MQ back to detectable coherence) efficiency can significantly be enhanced with DFS (Double Frequency Sweep) or FAM (Fast Amplitude Modulation) type pulses instead of rectangular pulse irradiation (Goldbourt and Madhu, 2002). In contrary to conversion, it is more challenging to enhance MQ excitation in MQMAS experiments, since most methods result in distorted lineshapes (Goldbourt and Madhu, 2002; Lim and Grey, 1998). In the present work MQ excitation of single crystals was studied, and the understanding of the process led to a principle, which was extended to the excitation of powder samples as well. The resulting method was implemented into the MQMAS sequence to enhance MQ excitation of powder samples under MAS condition. The new sequence called SFAM (Shifted Fast Amplitude Modulation) can provide high enhancements at low RF powers (ϵ>4 at νrf=40 kHz) compared to rectangular pulses. Although simulated lineshapes of SFAM predict only minor deviations from ideal lineshapes, experimentally obtained lineshapes along the anisotropic dimension show rather strong distortions. SFAM is relatively simple to optimize, and shows robustness with respect to the miscalibration or inhomogeneity of the RF power as well as to other parameters of the pulse scheme. A good agreement was found between numerically and experimentally optimized parameters.