Infrared spectroscopy of hydrogen-bonded CHCl3-SO2 in the gas phase

A molecular association between chloroform and sulfur dioxide in the gas phase at room temperature was studied by Fourier, transform infrared spectroscopy. Since the intensity of the CH-stretching fundamental vibration of monomer chloroform is very weak but much stronger upon complexation, a simple subtraction procedure isolated the CH-stretching vibration spectrum of the complex. The presence of a 1:1 complex was confirmed by two dilution series, where the monomer concentrations were varied. The molecular association manifested itself as a shift of the peak absorbance of the CH-stretching vibration of CHCl3-SO2 by +7 cm(-1) and of the CD-stretching vibration of CDCl3-SO2 by +5 cm(-1) to higher wave numbers compared to monomer chloroform, accompanied by a considerable broadening of the band contour. In agreement with previous ab initio calculations, this indicates a "blueshifting" or more appropriately, a "C-H contracting" hydrogen bond between chloroform and sulfur dioxide. An estimate of the complex concentration was made based on ab initio calculations for the integrated band strength and the measured spectrum. With this estimate, the equilibrium constant K-p (295 K) = 0.014 (p(o) = 10(5) Pa) for the dimerization was calculated, providing one of the very few cases where the formation of a hydrogen-bonded gas phase complex at room temperature could be quantitatively studied by infrared spectroscopy. (c) 2006 American Institute of Physics.