Analysis of the bound–free emission spectra from the E(0+) and f(0+) ion-pair states of ClF to obtain potentials for the ion-pair and repulsive valence states

Abstract

The optical–optical double resonance method has been used to excite selected vibrational levels of the E(0+) and f(0+) ion-pair states of ClF. Subsequent bound–free transitions terminating on three repulsive valence states, Y(3Σ0+−), B1(3Π0+), and C(1Σ0++), have been analyzed. The bound–free continua have been modeled to obtain analytical expressions for the three 0+ repulsive potentials and to improve the description for the E(0+) and f(0+) state potentials. One of the repulsive states is Y(3Σ0+−), which is responsible for the predissociation of B(3Π0+). The transition dipole functions also have been assigned for the bound–free transitions. The molecular orbital configurations of the lower states are discussed. Finally, the influence of homogeneous interaction between the E(0+) and f(0+) states on the bound–free spectra from certain vibrational levels is discussed.