Journal of Chemical Physics, Vol.120, No.10, 4852-4859, 2004
Extended rotational diffusion and orientational relaxation of symmetric top molecules in a strong dc electric field: Second-rank orientational correlation functions
Second-rank orientational correlation functions (pertaining to Kerr effect relaxation and Raman scattering) are obtained using the extended rotational diffusion (J-diffusion) model of symmetric top polar molecules in a strong constant external field. It is shown that the shape of the molecule noticeably affects all second-rank correlation functions and relaxation times in the rare collision limit. In the opposite limit of frequent collisions, the quantities of interest are shown to be shape independent as a consequence of vanishingly small inertial effects. An interpolation formula for the orientation relaxation times in the intermediate regime between the rare and frequent collision limits is also given. (C) 2004 American Institute of Physics.