PHOTOGENERATION OF IONIC SPECIES IN AR, KR AND XE MATRICES DOPED WITHHCL, HBR AND HI

Photogeneration of Ar2H+, Kr2H+ and Xe2H+ and their deuterated counter parts is reported in H(D)Cl doped Ar, and H(D)X(X=Cl, Br or I) doped K r and Xe matrices, respectively. The formation of these species is asc ribed to optical access of the delocalized X/rare gas charge transfer states, and subsequent charge trapping processes. Once generated, the absorptions of the cations bleach thermally at low temperatures (12 K) . The observed second-order decay kinetics is discussed in terms of ch arge-recombination involving a distribution of barrier heights. The de uterated cations bleach on a significantly longer timescale. Bihalide ions, HX(2)(-), of D-proportional to h symmetry are the other products formed in the photolysis. Annealing of the extensively irradiated HCl , HBr and HI doped xenon and HCl doped krypton yields strong infrared absorptions in the 1200-1600 cm(-1) spectral region. These bands are t entatively ascribed to linear asymmetric (X-H-X)- ions perturbed by a nearby positive charge, or to (XeHX)(+) and (KrHX)(+) species.