Imaging study of O3 photodissociation in the Huggins band

Abstract

We report a velocity-mapped ion imaging study of the photodissociation of O3 in the Huggins band. The O(3PJ) images show evidence for three electronic channels producing O2(X3Σg−), O2(a1∆g), and O2(b1Σg+) state fragments, with the latter two arising from the spin-forbidden photodissociation of O3. Forward convolution simulations of the derived total translational energy distributions permit extraction of the vibrational state distribution for each O2 electronic state. All these distributions peak near v = 0 and decrease monotonically with the vibrational state. The wavelength-dependent branching of the three electronic channels has been determined and is approximately constant over the wavelength region studied (322–328 nm). We have observed that the O2 electronic state branching ratios depend on the coincident O(3PJ) spin–orbit state, and the O2(b1Σg+) state is particularly sensitive. These results are qualitatively consistent with previous calculations on the coupling of the initially excited state to dissociative states by Rosenwaks and Grebenshchikov [J. Phys. Chem. A. 114, 9809–9819 (2010)]. The spatial anisotropy of the three dissociation channels has been determined through analysis of the O(3P0) angular distributions. The results are consistent with recent calculations but differ from previous experimental reports. The experimental results provide detailed information on the dissociation dynamics and should motivate new calculations.