Potential energy surfaces (PES) for rotation about the N-C(sp(3)) or N-C(aryl) bond and energies of stationary points on PES for rotation about the C(sp(2))-N bond are reported for methylthiourea, ethylthiourea, isopropylthiourea, tert-butylthiourea, and phenylurea, using the MP2/aug-cc-pVDZ method. Analysis of alkylthioureas shows that conformations, with alkyl groups cis to the Sulfur atom, are more stable (by 0.4-1.5 kcal/mol) than the trans forms. All minima adopt anti configurations with respect to nitrogen pyramidalization. whereas syn configurations are not stationary points on the MP2 potential surface. In contrast, analysis of phenylthiourea reveals that a trans isomer in a syn geometry is the global minimum, whereas a cis isomer in an anti geometry is a local minimum with a relative energy of 2.7 kcal/mol. Rotation about the C(sp(2))-N bond in alkyl and phenyl thioureas is slightly more hindered (9.1 - 10.2 kcal/mol) than the analogous motion in the unsubstituted molecule (8.6 kcal/mol). The maximum barriers to rotation for the methyl, ethyl, isopropyl, tert-butyl, and phenyl substituents are predicted to be 1.2, 8.9, 8.6. 5.3, and 0.9 kcal/mol, respectively. Corresponding PESs are consistent with the experimental dihedral angle distribution observed in crystal structures. The results of the electronic structure calculations are used to benchmark the performance of the MMFF94 force field. Systematic discrepancies between MMFF94 and MP2 results were improved by modification of selected torsion parameters and one of the van der Waals parameters for sulfur.