The gross requirement is an anisotropic polarizability tensor, so that changing molecular orientation changes the induced response. A permanent electric dipole moment is not required; a homonuclear diatomic can therefore have a rotational Raman scattering spectrum.
For the inelastic lines of a linear rigid rotor, the detailed rule is , with . The contribution is unshifted Rayleigh scattering, not a rotational Stokes Raman scattering line. Stokes Raman scattering has because the molecule gains rotational energy.
Because , the terms cancel between the initial and final states. The two positive-shift branches are consequently
The branch gives shifts , as for the diatomic. The branch fills in a series spaced by , so the combined nonzero series is .
There is a boundary qualification to the abbreviated rules printed in the question: for an ordinary symmetric polarizability tensor, has zero strength when . Thus does not produce a line; the first transition can start at and has shift . This follows from the rank-two angular-momentum coupling: the all-zero-projection coupling for and vanishes because is odd. If one applies only the printed inequalities without this matrix-element restriction, is a formal position, but its intensity is zero.
The lower panel of the figure in part (a)(ii) marks the two branches and their overlaps. The useful spacing is , not the diatomic value .
The D4h molecular point group contains an inversion centre, so infrared and Raman mutual exclusion applies. A normal mode of parity can have vibrational infrared activity, whereas the quadratic polarizability tensor components responsible for Raman vibrational activity have parity. No individual fundamental can be active in both spectra.
The Td molecular point group lacks an inversion centre. In particular, normal modes transform both as electric-dipole components and as off-diagonal polarizability tensor components, so they occur in both spectra. Coincident IR and Raman fundamentals therefore favour the tetrahedral structure; symmetry requires no such coincidences for the square. Weak or unresolved features can conceal coincidences experimentally, while accidental equality of different frequencies is not a violation of mutual exclusion.
In this C2v point group convention, , , and . Therefore all six normal modes have symmetry-allowed infrared fundamentals: , absent accidental coincidences or vanishing intensities.
For Raman spectroscopy, examine the polarizability tensor: , , and ; is also Raman-allowed but no vibration occurs here. All six vibrations are therefore Raman-active too, giving . The centrosymmetric mutual-exclusion rule does not apply to formaldehyde.