Photofragment angular momentum distribution beyond the axial recoil approximation: The role of molecular axis rotation

We present the quantum-mechanical expressions for the recoil angle dependence of the photofragment multipole moments which explicitly treat the role of molecular axis rotation on the electronic angular momentum polarization of the fragments. The paper generalizes the result of Siebbeles [ J. Chem. Phys. 100 , 3610 ( 1994 ) ] to the case of dissociation of rotating molecules. The electronic wave function of the molecule was used in the adiabatic body-frame representation. The obtained rigorous expressions for the fragment state multipoles have been explicitly derived from the scattering wave-function formalism and then simplified using the quasiclassical approximation in the high- J limit. Possible radial and Coriolis nonadiabatic interactions have been taken into consideration. It is shown that the rotation of the molecular axis is described by a number of rotation factors which depend on the rank of the incident-photon polarization matrix, on the dissociation mechanism, and on the classical angle of rotation of the molecular axis γ .