Collect. Czech. Chem. Commun. 1989, 54, 2555-2630

Forbidden transitions in molecular vibrational-rotational spectroscopy

Dušan Papoušek

The J. Heyrovský Institute of Physical Chemistry and Electrochemistry, Czechoslovak Academy of Sciences, 182 23 Prague 8


A review is given of the forbidden ( more precisely: perturbation allowed) transistions between molecular vibrational-rotational states including transistions which are induced by the electric dipole and quadrupole moments and the magnetic dipole moment. The basic theory of these transistions is outlined starting with the overall symmetry selection rules, followed by the discussion of the spin statistics isomers, approximate selection rules for the usual vibrational-rotational transistions, and forbidden transistions induced by the electric quadrupole and magnetic dipole moments. Forbidden transistions due to the vibrationally and rotationally induced electric dipole moments are the discussed in detail for symmetric top and spherical top molecules with the emphasis on the physical nature of the various phenomena leading to these transistions. A summary is also given of the most important experimental work on the forbidden transistions in diatomic molecules and polar as well as nonpolar polyatomics.