Journal of Chemical Physics, Vol.103, No.21, 9161-9174, 1995
Far-Infrared Permanent and Induced Dipole Absorption of Diatomic-Molecules in Rare-Gas Fluids .2. Spectral Theory
We present a spectral theory for the far-infrared absorption spectrum of a very diluted solution of diatomic molecules in a rare-gas fluid, that includes permanent and induced contributions. The absorption coefficient is given as the convolution of a translational spectrum and a rotational spectrum. The former is described in terms of time correlation functions associated to the induced dipole moment. The latter is discussed on the basis of a model consisting of a quantum rigid rotor interacting with a thermal bath, making use of time correlation functions associated to the different anisotropic orders of the solute-solvent intermolecular potential. Non-Markovian and line mixing effects are taken into account. Explicit expressions for the five leading contributions of the induced dipole moment are given.
Keywords:COLLISION-INDUCED ABSORPTION;TIME-ORDERING-CUMULANT;ROTATION BAND SHAPES;POLAR-MOLECULES;SIMPLE LIQUIDS;STATISTICAL PROPERTIES;RANGE INTERACTIONS;TRIPLET DIPOLES;NITROGEN;MIXTURES