Vector Correlations in the Photodissociation of CH3I, OCS, and Glyoxal

Abstract

AbstractThe use of vector correlations to elucidate the photodissociation dynamics of CH3I, OCS, and glyoxal is discussed. The correlations occur between the vectors Ě, the electric vector of the photolysis light, μ, the transition dipole moment of the parent, v, the relative recoil velocity of the fragments, and J, the angular momentum of one of the fragments. The Ě – μ – v correlation is illustrated by a direct imaging technique in the photodissociation of CH3I; it shows that dissociation takes place by a parallel transition and is rapid compared to parent rotation. The “triple vector correlation”, Ě – μ – (v – J), is used to show that the dissociation of OCS proceeds on two surfaces, one of A″ and one of A′ symmetry in the Cs point group. The v – J correlation in the dissociation of glyoxal illustrates two points, that dissociation of this molecule takes place in a plane and that vector correlations can exist even for dissociations which are slow compared to parent rotation.