Electronic Angular Momentum Polarizations of Atomic Fragments in Diatomic Photodissociations: Correlations between Electronic States in the Molecular and the Asymptotic Regions

Abstract

AbstractTo understand electronic angular momentum polarization phenomena of atomic photofragments in diatomic photodissociations, Wigner‐Witmer correlation rules should be augmented to treat these problems quantitatively. The essential step to achieve this goal is to find the transformation relationships between basis functions of Hund's coupling cases (a) (or (b)) and (c). Because the partition of a united electronic configuration into two separated electronic configurations is undertaken, in general no analytical transformation can be established. To illustrate the present scheme in acquiring the transformation relationships, the direct photodissociation of O2(B3Σ−u) into O(1D) + O(3P) is explicitly considered. The electronic angular momentum polarization of oxygen atoms in |1D, J = 2, MJ = 0〉 observed in the recent experiment on O2 photodissociation can be rationalized by this quantitative correlation rule.