We present a quantum chemical ab initio study which demonstrates a new combined experimental and theoretical approach, whereby a comparison of calculated and experimental H-1 NMR chemical shifts allows the elucidation of structural arrangements;in solid-state molecular ensembles, taking advantage of the marked sensitivity of the H-1 chemical shift to intermolecular interactions. Recently, Brown et al, have shown that, under fast magic-angle spinning (MAS) at 35 kHz, the resolution in a H-1 NMR spectrum of the solid phase of an alkyl-substituted hexabenzocoronene (HBC) derivative is sufficient tb-observe the hitherto unexpected resolution of three distinct aromatic resonances ( J. Am. Chem. Sec. 1999, 121, 6712. Exploiting the additional information about proton proximities provided by H-1 double-quantum (DQ) MAS NMR spectroscopy, it was shown that the results are qualitatively consistent with the aromatic cores packing in a manner similar to that in unsubstituted HBC. Using the HBC-C-12 molecule as an example, we show here that the new combined experimental and theoretical approach allows the observed H-1 chemical shifts to be related in a quantitative manner to the intermolecular structure. In the quantum chemical calculations, a series of model systems of stacked HBC oligomers are used. On:account of the marked dependence of the H-1 chemical shift to ring currents arising from nearby aromatic rings, the calculated H-1 chemical shifts are found to be very sensitive to the stacking arrangement of the HBC molecules. Moreover, the ring current effect is found to be particularly long range, with a considerable influence of the second neighbor, at a distance of 700 pm, being observed.