Infrared absorption and predissociation of NO dimer

Abstract

The infrared absorption spectrum of the ν4 fundamental band of (NO)2 has been recorded at 0.3 cm−1 resolution in a cell cooled down to 110 K. From the band contour analysis and comparison with a simulated spectrum accurate values of the rotational constants in the ν4 state are derived, showing a reduction of the van der Waals bond on vibrational excitation. Absorption measurements performed using the various lines emitted by an isotopic CO laser suggest an unresolved rotational fine structure. A lower limit of the time for energy redistribution of 50 to 100 ps is proposed. Also, infrared photopredissociation of (NO)2 has been directly observed in a crossed laser-molecular beam experiment using bolometric detection of the beam attenuation. An upper limit of the dissociation lifetime can be set to 10−3 s.