Vibrationally mediated photodissociation of t-butyl hydroperoxide: Vibrational overtone spectroscopy and photodissociation dynamics

Abstract

Vibrationally mediated photodissociation is a two‐photon technique for studying the spectroscopy and photodissociation dynamics of highly vibrationally excited molecules. In these experiments, a highly vibrationally excited t‐butyl hydroperoxide (t‐BuOOH) molecule, prepared by excitation in the region of the third overtone of the O–H stretching vibration (4νOH), absorbs a second photon to dissociate to OH and t‐butoxy fragments, and laser induced fluorescence determines the quantum state populations of the OH fragment. Vibrational overtone excitation spectra, obtained by varying the vibrational overtone excitation wavelength while monitoring a single OH rotational state, are nearly identical to photoacoustic spectra. We fit the coarse structure in the vibrational overtone excitation spectrum in the region of the 4νOH transition and the photoacoustic spectra in the regions of the 5νOH and 6νOH transitions using a spectroscopic model of the interaction of the O–H bond stretching vibration with the torsional vibration about the O–O bond. This analysis determines the barrier to internal rotation of the O–H and t‐butoxy groups through the t r a n s configuration and its variation with vibrational excitation. The t r a n s barrier in the ground vibrational state is 275 cm− 1 and increases with vibrational excitation to 425, 575, and 680 cm− 1 for t‐BuOOH molecules with four, five, and six quanta of O–H stretching excitation, respectively. Comparison of the energy disposal in the vibrationally mediated photodissociation with that for direct photolysis at 376 nm, which adds the same amount of energy to the molecule, illustrates the unique dynamics that can occur when vibrational excitation precedes photodissociation. Single‐photon photolysis produces fragments with large recoil velocities, while vibrationally mediated photodissociation produces slowly recoiling fragments having substantially more energy in internal excitation.