Vacuum Ultraviolet Photodissociation Branching Ratios of 12C16O, 13C16O, and 12C18O from 100500 to 102320 cm-1.

The C+ ion photofragment spectra and photodissociation branching ratios into the two energetically available channels, C(1D) + O(3P) and C(3P) + O(3P), have been obtained for the three CO isotopologues, 12C16O, 13C16O, and 12C18O, in the vacuum ultraviolet range 100500-102320 cm-1. The two vibronic states of 1Σ+ symmetry, F(3dσ) 1Σ+(υ' = 1) and J(4sσ) 1Σ+(υ' = 0), predominantly dissociate into the lowest channel C(3P) + O(3P) through interactions with the repulsive D'1Σ+ state. All three vibronic states of 1Π symmetry, E'1Π(υ' = 1, 2) and G(3dπ) 1Π(υ' = 0), dissociate into both of the channels above. The photodissociation branching ratios into the channel C(1D) + O(3P) for E'1Π(υ' = 1, 2) are found to be independent of both the rotational quantum number and e/f parity, while those for G(3dπ) 1Π(υ' = 0) strongly depend on the rotational quantum number, indicating very different predissociation pathways between the valence states E'1Π(υ' = 1, 2) and the Rydberg state G(3dπ) 1Π(υ' = 0). The potential energy curves of CO in the aforementioned energy range and below have recently been well constructed due to a series of interplays between high-resolution spectroscopic studies and theoretical calculations; the photodissociation branching ratios measured in this study can provide further benchmarks for future theoretical investigations which aim to understand the detailed predissociation dynamics of CO.