Transitions between rotational states can be observed in molecules with a permanent electric dipole moment. A consequence of this rule is that no microwave spectrum can be observed for centrosymmetric linear molecules such as  (dinitrogen) or HCCH (ethyne), which are non-polar. Tetrahedral molecules such as  (methane), which have both a zero dipole moment and isotropic polarizability, would not have a pure rotation spectrum but for the effect of centrifugal distortion; when the molecule rotates about a 3-fold symmetry axis a small dipole moment is created, allowing a weak rotation spectrum to be observed by microwave spectroscopy.
With symmetric tops, the selection rule for electric-dipole-allowed pure rotation transitions is , . Since these transitions are due to absorption (or emission) of a single photon with a spin of one, conservation of angular momentum implies that the molecular angular momentum can change by at most one unit. Moreover, the quantum number K is limited to have values between and including +J to -J.