Intensities in local mode overtone spectra: Propane

Abstract

The gas phase vibrational overtone spectrum of propane is measured using conventional near infrared (NIR) spectroscopy for the Δv CH=2–5 regions and intracavity dye laserphotoacoustic spectroscopy (IDL‐PAS) for the Δv CH=5 and 6 regions. The peaks are assigned in terms of the local mode model. Experimental oscillator strengths are compared to values calculated for the CH‐stretching components of the spectrum. The calculations use a harmonically coupled, anharmonic oscillator local mode model to obtain the vibrational wave functions, and a b i n i t i o MO calculations at the SCF level with a 6‐31G* basis set to obtain the dipole moment function. The importance of intermanifold coupling is explored. The calculations can account for the fall‐off in intensity with increasing v, and can give a reasonably quantitative account of the relative intensities of the individual peaks within a given vibrational manifold. The questions of the relative intensities of primary and secondary CH bonds, and of the relative intensities of different methyl CH bonds are also explored.