Photodissociation dynamics of Cl2O at 235 nm using velocity map ion imaging

We have investigated the photodissociation dynamics of expansion-cooled Cl2O at 235 nm using photofragment velocity map ion imaging coupled with resonance-enhanced multiphoton ionization (REMPI) to measure the speed and angular distributions of the Cl(2P3/2) and Cl(2P1/2) products. We observe speed-dependent spatial anisotropy for both Cl fragments from the imaging data and attribute this to a fraction of nascent ClO, which undergoes secondary photodissociation. We have employed a Monte–Carlo forward-convolution scheme to analyze the data and obtain the speed distribution and anisotropy parameters for the ClO + Cl(2P3/2,1/2) channels. We find that the speed distribution of the Cl(2P3/2) + ClO channel is bimodal with an anisotropy parameter of 1.2 ± 0.2, whereas the speed distribution of the Cl(2P1/2) + ClO channel consists of a single component with an anisotropy parameter of 1.0 ± 0.2. We have determined branching ratios for Cl(2P3/2) + ClO and Cl(2P1/2) + ClO channels to be 0.97 ± 0.02:0.03 ± 0.02. Based on the translational energy distribution of Cl(2P3/2) + ClO channel, 28% of the parent molecule undergoes three-body dissociation.

► Photodissociation dynamics of Cl2O at 235 nm using ion imaging.
► Speed-dependent anisotropy parameters were observed.
► Secondary photodissociation and three-body dissociation were modeled to fit data.