Selective excitation in Fourier transform nuclear magnetic resonance

The applications of frequency-selective excitation methods in Fourier transform NMR are discussed, and a simple technique is described for selective excitation of a narrow frequency region of a high-resolution NMR spectrum in a Fourier transform spectrometer. A regular sequence of identical radiofrequency pulses of small flip angle exerts a strong cumulative effect on magnetizations close to resonance with the transmitter frequency or one of a set of equally spaced sidebands separated by the pulse repetition rate. All other magnetizations precess through an incomplete number of full rotations between pulses, and are caught by successive pulses at an ever changing phase of their precession, which destroys the cumulative effect. The motion of the various nuclear magnetization vectors may be described pictorially according to the Bloch equations, neglecting relaxation during the pulse sequence. A general theory is presented for selective or “tailored” excitation by an arbitrary modulation of the radiofrequency transmitter signal. It confirms earlier conclusions that the frequency-domain excitation spectrum corresponds to the Fourier transform of the transmitter modulation pattern, provided that the NMR response remains linear. The excitation spectra calculated for the selective pulse sequence by these two alternative approaches show good agreement within their respective limitations. A number of practical applications of selective excitation are explored, including solvent peak suppression, the detection of partial spectra from individual chemical sites, selective studies of relaxation and slow chemical exchange, and holeburning or localized saturation.