The complete harmonic force field of pyrimidine has been computed at the ab initio Hartree-Fock level using a 4-21 Gaussian basis set. In order to compensate the systematic overestimations of the force constants at the aforementioned level of quantum mechanical approximation, the theoretical force constants were empirically scaled by using nine scale factors. (The values of all these scale factors were previously determined by fitting the theoretical force field of benzene to the observed vibrational spectra of benzene.) The resulting a priori scaled quantum mechanical (SQM) force field is regarded as the most accurate and physically the most correct harmonic force field for pyrimidine. This force field was then used to predict the vibrational spectra of pyrimidine-h4 and pyrimidine-d,. On the basis of these a priori vibrational spectra uncertain assignments have been confidently resolved. After a few reassignments, the mean deviations between the experimental and calculated frequencies are below 9 and 18 cm-' for the non-CH stretching in-plane and the out-of-plane vibrations, respectively. Computed IR intensities are generally in agreement with experiments at a qualitative level.