Photodissociation study of CO2 on the formation of state-correlated CO(X1S???????+, v) with O(3P2) photoproducts in the low energy band centered at 148 nm

The spin-forbidden O(P-3(2)) + CO(X-1 sigma(+), v) channel formed from the photodissociation of CO2 in the low energy band centered at 148 nm is investigated by using the time-sliced velocity-mapped ion imaging technique. The vibrational-resolved images of the O(P-3(2)) photoproducts measured in the photolysis wavelength range of 144.62-150.45 nm are analyzed to give the total kinetic energy releases (TKER) spectra, CO(X-1 sigma(+)) vibrational state distributions, and anisotropy parameters (beta). The TKER spectra reveal the formation of correlated CO(X-1 sigma(+)) with well resolved v = 0-10 (or 11) vibrational bands. Several high vibrational bands that were observed in the low TKER region for each studied photolysis wavelength exhibit a bimodal structure. The CO(X-1 sigma(+), v) vibrational distributions all present inverted characteristics, and the most populated vibrational state changes from a low vibrational state to a relatively higher vibrational state with a change in the photolysis wavelength from 150.45 to 144.62 nm. However, the vibrational-state specific beta-values for different photolysis wavelengths present a similar variation trend. The measured beta-values show a significant bulge at the higher vibrational levels, in addition to the overall slow decreasing trend. The observed bimodal structures with mutational beta-values for the high vibrational excited state CO((1)sigma(+)) photoproducts suggest the existence of more than one nonadiabatic pathway with different anisotropies in the formation of O(P-3(2)) + CO(X-1 sigma(+), v) photoproducts across the low energy band.

Automated summary

The spin-forbidden O(P-3(2)) + CO(X-1 sigma(+), v) channel formed from the photodissociation of CO2 in the low energy band centered at 148 nm is investigated. The vibrational-resolved images of the O(P-3(2)) photoproducts are analyzed to determine the TKER spectra, CO(X-1 sigma(+)) vibrational state distributions, and anisotropy parameters (beta). The results show the formation of correlated CO(X-1 sigma(+)) with specific vibrational bands and reveal a bimodal structure in the high vibrational bands.