An experiment is described that utilizes the truncation of the Hamiltonian in the rotating frame by a radio‐frequency field designed to yield an isotropic shift for the dipolar coupling. This approach allows the measurement of a normally orientation‐dependent coupling constant by a single isotropic value. The dipolar isotropic shift is closely related to the field‐dependent chemical shift in solids due to the second‐order dipolar perturbation observed in magic‐angle spinning experiments. In the rotating frame, larger shifts of up to 1000 Hz can be observed for the case of a one‐bond C–H coupling compared to a shift of a few Hertz in the laboratory‐frame experiment. In addition to the isotropic shift, a line broadening due to the P4(cos β) terms is observed when the experiment is carried out under magic‐angle sample spinning (MAS) conditions, leading to the requirement of higher‐order averaging such as double rotation (DOR) for obtaining narrow lines. As an application of this new experiment the separation of CH, CH2, and CH3 groups in a 2D spectrum under MAS is demonstrated. Implemented under DOR it could be used as a technique to select carbon atoms according to the number of directly attached protons.

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