Observation of bound-free transitions of the linear Ar⋯I2(X,v″=) complex in and above the I2B-X spectral region

Abstract

Laser-induced fluorescence and action spectroscopy experiments were performed to identify the origin of the Ar...I(2) continuum signals observed in and above the I(2) B-X spectral region. We have verified that these signals arise from transitions of the linear Ar...I(2) (X,v"=0) complex. The data provides no evidence that the excited state complexes undergo a one-atom caging mechanism when prepared above the I(2)(B) dissociation limit, Ar...I(2) (B)*-->Ar+I+I*-->Ar+I(2)(B,v'). Instead, our results indicate that the continuum signals result from bound-free transitions of the linear Ar...I(2) X,v(")=0) complex to the inner repulsive walls of numerous Ar+I(2)(B,v') intermolecular potentials. The bound-free continuum signal associated with transitions to each Ar+I(2)(B,v') potential spans an energy region >700 cm(-1). We have found that the continuum signals turn-on 250(2)cm(-1) above the corresponding I(2) B-X,v'-0 band origin, and this energy represents the binding energy of the linear Ar...I(2) (X,v"=0) conformer, D(0) (")(L)=250(2)cm(-1).