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Keywords:

  • energy-level diagrams;
  • NMR spectroscopy;
  • progressive connectivity;
  • regressive connectivity;
  • spin tickling

Abstract

In the long bygone days of continuous-wave nuclear magnetic resonance (NMR) spectroscopy, a selected transition within a multiplet of a high-resolution spectrum could be irradiated by a highly selective continuous-wave (CW) radio-frequency (rf) field with a very weak amplitude equation image/(2π)≤J. This causes splittings of connected transitions, allowing one to map the connectivities of all transitions within the energy-level diagram of the spin system. Such “tickling” experiments stimulated the invention of two-dimensional spectroscopy, but seem to have been forgotten for nearly 50 years. We show that tickling can readily be achieved in homonuclear systems with Fourier transform spectrometers by applying short pulses in the intervals between the sampling points. Extensions to heteronuclear systems are even more straightforward since they can be carried out using very weak CW rf fields.