predissociation

Dissociation occurring by tunnelling from a 'bound' to an 'unbound' vibronic state. In an absorption spectrum of a molecular entity, the appearance of a diffuse band region within a series of sharp bands is called predissociation, since irradiation with frequencies within the diffuse region leads to effective dissociation. The energy of the band is smaller than that of the dissociation continuum of the bound state.