Through-space spin-spin coupling in van der waals dimers and CH/π interacting systems.: An ab initio and DFT study

The through-space J(HH) and J(CH) spin-spin coupling constants of model van der Waals dimers (involving methane. ethylene, and benzene). and of selected compounds showing, the CH/pi interaction. have been investigated by means of DFT and ab initio calculations. In the range of intermolecular separations for which the interaction is stabilizing. weak couplings (0.1-0.3 Hz) Lire predicted for J(CH), while the corresponding J(HH) couplings are much smaller. The relative contributions (Fermi-contact. spin-orbit, and spin-dipole) are strongly dependent on the geometry of the dimers and on the distance: the non-negligible values of J(CH) for T systems stem largely from an incomplete cancellation of spin-orbit terms. The results obtained for the larger molecules, that is. acetoniktrile@calix[4] are ne 5, the imine 6. and the aryl ester 7 are consistent with those on the model dimers. For 7, the occurrence of a through-space mechanism for the transmission of coupling is established by examining trends in the magnitude of couplings as a function of the number of intervening covalent bonds.