A molecular dynamics simulation has been carried out of biphenyl dissolved in a solvent comprised of rigid particles interacting with the Gay–Berne potential. The solution is investigated in isotropic, nematic, and smectic phases, and the probability distribution, PLC(φ) obtained, where φ is the angle between the two ring normals. This is compared with Pmol(φ), the distribution calculated for an isolated molecule, and it is found that the positions, φmax of the maxima of the two distributions differ by about 2°. The molecular dynamics trajectory is used to calculate averaged nuclear spin dipolar couplings, Dij, and these are used to test the maximum entropy (ME) and additive potential (AP) theoretical models which have been used previously to obtain the distribution PLC(φ) from dipolar couplings obtained on real solutions of biphenyl in liquid crystalline solvents. It is concluded that the AP method is able to recover the true distribution PLC(φ) from the simulated Dij with good precision at all the temperatures studied, whereas the ME method achieves good precision only when the orientational order is high. The AP method also succeeds in obtaining the correct difference between PLC(φ) and Piso(φ), the distribution for an isotropic phase at the same temperature.