Multiplet patterns due to co-existing intermolecular dipolar and intramolecular scalar couplings in liquid nuclear magnetic resonance

When both intermolecular dipolar couplings (D couplings) and intramolecular scalar couplings (J couplings) exist in a highly polarized multiple-spin liquid, some forbidden nuclear magnetic resonance signals originating from intermolecular multiple-quantum coherences may become observable. Moreover, their multiplet patterns are quite different from what are observed in a multiple-spin system with J couplings only. In this paper, these forbidden resonance peaks and unique multiplet patterns are studied theoretically and experimentally. For comparison and verification, an I₂S₃+X spin system is chosen as an example to present five types of signal patterns from the interactions of D and J couplings with either selective or non-selective radio-frequency pulse sequences for double-quantum coherences. The multiplet pattern rules for a more general I_pS_q+X_k (p, q, k=1, 2, 3,…) spin system are derived as well. It is demonstrated that some unusual multiplet amplitude patterns such as (1:0:—1) may "magnify" J splittings, allowing more accurate measurement of J coupling in the case of small J coupling constants and/or in inhomogeneous fields. It is shown that the theoretical predictions, computer simulations, and experimental observations are all in agreement with one another very well.