Equilibrium structural constants and certain torsion-rotation interaction parameters have been determined for methanol and acetaldehyde from ab initio calculations using GAUSSIAN 94. The substantial molecular flexing which occurs in going from the bottom to the top of the torsional potential barrier can be quantitatively related to coefficients of torsion-rotation terms having a (1-cos 3 gamma) dependence on torsional angle gamma. The barrier height, six equilibrium structural constants characterizing the bottom of the potential well, and six torsion-rotation constants are all compared to experimental parameters obtained from global fits to large microwave and far-infrared data sets for methanol and acetaldehyde. The rather encouraging agreement between the Gaussian and global fit results for methanol seems both to validate the accuracy of ab initio calculations of these parameters, and to demonstrate that the physical origin of these torsion-rotation interaction terms in methanol lies primarily in structural relaxation with torsion. The less satisfactory agreement between theory and experiment for acetaldehyde requires further study.