Photodissociation of polarized diatomic molecules in the axial recoil limit: Control of atomic polarization

A quantum mechanical treatment of the photofragment angular momentum polari zation following photodissociation of diatomic molecules is presented. This treatment extends that of Siebbeles [J. Chem. Phys. 100, 3610 (1994)] by c onsidering photodissociation of a molecule whose angular momentum is polari zed in the laboratory frame, and also treats properly the angular momentum coupling between the two photofragments. The formalism treats coherent exci tation of dissociative surfaces and the consequences of nonadiabatic coupli ng between surfaces. The possibility of exploiting the parent molecule pola rization in order to control the photofragment polarization when both paral lel- and perpendicular-type dissociations are active is discussed. An examp le is given in which significant control over the molecular frame polarizat ion of the fragments is achieved following photolysis of a parent molecule prepared by an electric dipole transition, which may be of use in the study of photoinitiated bimolecular reactions. (C) 2000 American Institute of Ph ysics. [S0021-9606(00)00540-7].