Proton radiolysis of CHCl3 and CHBr3 at high dilution in argon during condensation at 15 °K. Infrared spectra of the CHX+2, CHX−2, and CHX−3 molecular ions

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Matrix samples of chloroform and its deuterium and bromine analogs have been subjected to irradiation by a 2.0 keV proton beam during deposition, and the products trapped in an argon matrix at 15 °K. Several infrared absorptions have been observed and assigned to a number of new molecular species. Extremely photosensitive bands observed at 652, 621, 593, and 570 cm−1 have been assigned to the CHCl−3, CHCl2Br−, CHClBr−2, and CHBr−3 molecular anions, respectively. Absorptions at 998, 907, and 839 cm−1, which were decreased by operating an exposed bulb filament, have been attributed to the isolated cations CHCl+2, CHClBr+, and CHBr+2. Bands stable to the bulb filament at 1044, 988, and 898 cm−1 were assigned to the CHX+2 (X−) species and similar bands at 838, 795, and 735 cm−1 were assigned to the CHX2− anions. In addition, bands attributable to the species CX3, CX2CX3+(X−), CHX2, and HX−2, which have been identified previously, were observed here as well.