Journal of Physical Chemistry A, Vol.122, No.41, 8136-8142, 2018
Branching Ratio Measurements of the Predissociation of (CO)-C-12-O-16 by Time-Slice Velocity-Map Ion Imaging in the Energy Region from 106 250 to 107 800 cm(-1)
Photodissociation of CO is a fundamental chemical mechanism for mass-independent oxygen isotope fractionation in the early Solar System. Branching ratios of photodissociation channels for individual bands quantitatively yield the trapping efficiencies of atomic oxygen resulting into oxides. We measured the branching ratios for the spin-forbidden and spin-allowed photodissociation channels of (CO)-C-12-O-16 in the vacuum ultraviolet (VUV) photon energy region from 106 250 to 107 800 cm(-1) using the VUV laser time-slice velocity-map imaging photoion technique. The excitations to four (1)Pi bands and three (1)Sigma(+) bands of (CO)-C-12-O-16 were identified and investigated. The branching ratios for the product channels C(P-3) + O(P-3), C(D-1) + O(P-3), and C(P-3) + O(D-1) of these predissociative states strongly depend on the electronic and vibrational states of CO being excited. By plotting the branching ratio of the spin-forbidden dissociation channels versus the excitation energy from 102 500 to 110 500 cm(-1) that has been measured so far, the global pattern of the (1)Pi-(3)Pi interaction that plays a key role in the predissociation of CO is revealed and discussed.