Collisions of O(1D) with HCl, Cl2, and COCl2: Total quenching, channel specific rate constants, and yields of Cl(P1/22)

The method of time-resolved laser magnetic resonance was used to monitor Cl atoms produced by the reactions of O(D1) with HCl, Cl2, and COCl2 at room temperature. For these reactions, the measured relative quantum yields of spin-orbit excited atoms are [Cl(P1/22)]/([Cl(P1/22)]+[Cl(P3/22)])=(0.10±0.04), <0.05, <0.10, respectively. The rate constants for total removal of O(D1) by HCl, Cl2, and COCl2 have been determined to be (1.5±0.3), (2.5±0.5) and (2.6±0.5), respectively. The reactive rate constants have been determined to be k2=(0.94±0.2), k4=(1.9±0.3), and k5a+2k5b=(2.1±0.27); here k2, k4, k5a, and k5b are rate constants of O(D1)+HCl → OH+Cl (2), O(D1)+Cl2 → ClO+Cl (4), and O(D1)+ COCl2 → CO+ClO+Cl (5a), CO2 +2Cl (5b), respectively. The rate constants are in units of 10−10 cm3/molecule⋅s, quoted errors are 2σ.