Anisotropy of photofragment recoil as a function of dissociation lifetime, excitation frequency, rotational level, and rotational constant

Abstract

Quantum mechanical calculations of photofragment angular distributions have been performed as a function of the frequency of excitation, the lifetime of the dissociative state, the rotational level, and the rotational constant. In the limit of high J values and white, incoherent excitation, the general results are found to agree exactly with both those of Mukamel and Jortner [J. Chem. Phys. 61, 5348 (1974)] and those of Jonah [J. Chem. Phys. 55, 1915 (1971)]. Example calculations describe how the anisotropy is dependent on the degree of broadening, the rotational constant, the initial rotational level, and the frequency of excitation. Applications are also made to interpret experimental results on the photodissociation of ClO via the 11-0, 10-0, and 6-0 bands of the A 2Pi3/2 -X 2Pi3/2 transition and on the photodissociation of O2 via the 0-0 band of the E 3Sigmau- -X 3Sigmag- transition.