Rotational Raman spectroscopy ($\Delta J=0,\pm 2$)

Rotational Raman spectroscopy observes a frequency change of scattered light associated with molecular rotation. The coupling uses the induced electric dipole moment, ${\mathbf{d}}_{\mathrm{ind}}=\mathbf{\alpha }\mathbf{E}$, where $\mathbf{\alpha }$ is the electric polarizability tensor. For a linear molecule, the useful anisotropy is ${\alpha }_{\parallel }-{\alpha }_{\perp }$: the response differs for an electric field parallel or perpendicular to the molecular axis. A permanent electric dipole moment is not required.^[ref]

For the spin-free linear rigid rotor in one internal quantum state, the anisotropic tensor depends quadratically on the molecular direction. Its angular part has even parity and degree two in spherical harmonics. The triangle inequality for coupled angular momenta permits $|\Delta J|\le 2$, and even parity removes odd $\Delta J$, leaving $\Delta J=0,\pm 2$. The $\Delta J=0$ contribution is unshifted light; shifted rotational lines have $\Delta J=\pm 2$. Consequently the rigid-model Stokes shifts, in ordinary frequency units, areSuccessive allowed shifts are separated by $4B$, rather than the $2B$ absorption spacing of pure rotational electric-dipole selection rules. In spectroscopic wavenumber units replace $B$ by $\tilde{B}=B/c$ and $\Delta \nu$ by $\Delta \tilde{\nu }=\Delta \nu /c$, using the speed of light in $\mathrm{cm}{\mathrm{s}}^{-1}$ for $\mathrm{c}{\mathrm{m}}^{-1}$.

A homonuclear diatomic molecule such as molecular hydrogen has no permanent electric dipole moment in its symmetric internal state, so it lacks the ordinary electric-dipole microwave ladder. Its anisotropic electric polarizability can nevertheless give rotational Raman spectroscopy lines. Nuclear-spin symmetry can change the populations of even and odd $J$ levels, so the spin-free population example above must not be reused unchanged for molecular hydrogen. The method of coupling, as well as the energy eigenvalues, determines what the experiment can see.