IR spectroscopy of physical and chemical transformations in cold hydrogen chloride and ammonia aerosols

Aerosol particles of hydrogen chloride corresponding to three distinct solid phases have been generated in a collisional cooling cell and observed via FTIR spectroscopy. The cubic phase of HCl was observed with cell temperatures of 90-100 K, while the highly ordered orthorhombic phase predominated below this temperature. The previously reported metastable phase was also observed under some conditions. Density functional theory calculations at the B3LYP/6-311+G(d,p) level were performed on HCl clusters with a planar, zig-zag arrangement. Computed IR spectra for chain lengths up to 15 converge to show a band shape that is characteristic of the orthorhombic HCl phase. Injection of water along with HCl was found to have little influence on the formation of HCl particles. The reaction between HCl and NH3 to produce NH4Cl particles was also examined and found to occur over a wide range of temperatures (80-300 K). The formation of homogenous particles of HCl and NH3 competed with this chemical reaction as the cell temperature was lowered and when higher pressures of N2 buffer gas were used.