We describe several improvements to the reaction field model for the ab initio determination of solvation effects. First, the simple spherical cavity model is expanded to include higher-order electrostatic interactions. Second two new and efficient implementations of the polarizable continuum model (PCM) are described, which allow a more realistic specification of the solute cavity as well as infinite-order electrostatics. Electron correlation effects are evaluated using the B3LYP density functional and Moller-Plesset perturbation theory to second order. An assessment of the importance of these various factors is made by comparing theoretical results to the experimentally known conformational equilibrium between syn and anti forms of furfuraldehyde and the C-C rotational barrier of (2-nitrovinyl)amine. Comparisons are also made with calculations that employ an ellipsoidal cavity with sixth-order electrostatics. Optimization using a simple Onsager model appears to be sufficient to evaluate the important geometry changes in solution. Energies obtained from the spherical and ellipsoidal cavity models often exhibit poor convergence in the truncated electrostatic series. Correlation to experiment is much improved when an infinite-order PCM method is used.