Absolute Infrared Intensities in Some Crystalline Hydrogen Halides

Abstract

Absolute intensities of the fundamental vibrational bands of HCl and HBr have been measured in the absorptionspectrum of crystalline films. The path length has been determined from the interference fringes of the transmitted light as the film is deposited on a window, following the technique of Hollenberg and Dows. The measured integrated molar absorption coefficientsB are 24 000±3000 and 17 600±1200 darks (cm—1cm2/mM), respectively, for HCl and HBr. These values are larger than the gas phase intensities by factors of 6 and 13, respectively. Such large intensification of an X—H stretching vibration is consistent with the large frequency shift and is characteristic of hydrogen‐bonded crystals. The results are compared with those from other hydrogen‐bonded systems. Furthermore, the high intensities are consistent with those required by Hornig and Hiebert using the transition dipole—transition dipole model to explain the observed intermolecular force constants. However, it is likely that other terms contribute as much to these constants. Finally, the formalism used by Hexter to express the frequencies in molecular crystals is modified slightly so that hydrogen‐bonded crystals can be treated.