It has been shown that the shape of molecules, represented by the calculated molecular charge distribution, is a valuable source of information about the nature of the potential between molecules. For solid N2O, calculations based on the Kihara and the isotropic and anisotropic site–site potential models have shown that details of the molecular shape affects the relative stability of cubic, tetragonal, and orthorhombic phases at various pressures. This and details of the utilization of experimental data to characterize the potential show that features of CO2 are also described. Also, a Monte Carlo calculation, using a random variable to simulate the end‐to‐end disorder of solid N2O, conclusively shows that the average structure is Pa3 at low pressure and Cmca above 4.75 GPa.