Vibrational energy disposal by reaction of Xe(6s, 3P2) metastable atoms with chlorine containing molecules

Abstract

The bound–free XeCl spectra observed from the reactions of Xe(6s, 3P2) atoms with Cl2, PCl3, CCl4, and COCl2 have been compared to computer simulated spectra in order to assign the XeCl* vibrational energy distributions from these reactions. The 〈fV〉 values for the initial state distributions are between 0.6–0.8 for Cl2 and CCl4 and 0.2–0.3 for COCl2. The results for PCl3 are unusual in that the distribution for the XeCl (B) and XeCl (C) states apparently differ, with the 〈fV values being ∼0.47 and 0.64, respectively. This selection of reactions represents most types of XeCl spectra that have been observed and the vibrational energy disposal to XeCl by other Xe( 3P2) + RCl reactions can be estimated by comparison with these results. Model potentials, as well as the ab initio potentials of Hay, were used to represent the XeCl states for the simulation. Simulations were done for both the XeCl (B,1/2–X,1/2) and for the XeCl (C,3/2–A,3.2) transitions. The XeCl (B,1/2–X,1/2) transition is the more useful for assigning vibrational distributions because it is less sensitive to the shape of the lower potential. The dependence of the derived vibrational distributions upon the XeCl potentials and the variation of the transition moment with internuclear separation is discussed. The vibrational energy disposal for Xe ( 3P2)+Cl2 also is compared to that for Xe ( 3P2)+F2 and Kr ( 3P2)+F2.