Journal of Physical Chemistry A, Vol.113, No.26, 7621-7629, 2009
The Cl + H-2 -> HCl plus H Reaction Induced by IR plus UV Irradiation of Cl-2 in Solid para-H-2: Experiment
We report IR + UV coirradiation photolysis experiments conducted on Cl-2-doped para-hydrogen (p-H-2) crystals at 1.8 K, using pulsed 355 nm UV radiation and cw broad-band near-IR light from a FTIR tungsten source. The amount of HCl photoproduct is monitored using FTIR spectroscopy as a function of the IR + UV exposure time. Detailed analysis of the HCl growth kinetics reveals that the reaction Cl + H-2(v=1,J=0) -> HCl + H is playing a significant (15%) role in the in situ photochemistry. In contrast, UV-only photolysis experiments conducted under similar conditions produce almost exclusively (99%) isolated Cl atom photofragments, indicating the reaction Cl + H-2(v=0,J=0) -> HCl + H is not readily occurring. This combination of photolysis experiments confirms that under these conditions, the Cl + H, reaction probability increases by a factor greater than 25 for Cl atom reactions with H-2(v=1) versus H-2(v=0). These results are therefore consistent with the expectation that vibrational excitation of the H-2 reagent lowers the reaction threshold and increases the reaction cross section for the Cl + H-2 reaction. These experimental studies were motivated by and are compared to the quantum model simulations reported by Korolkov, Manz, and Schild in the accompanying paper.