The eΠg3 state of C 2 : A pathway to dissociation.

The lowest 13 vibrational levels, v = 0-12, of the eΠg3 state of the C ₂ molecule have been measured by laser-induced fluorescence of new bands of the Fox-Herzberg system. The newly observed levels, v = 5-12, which span the eΠg3 electronic state up to and beyond the first dissociation threshold of C ₂ , were analyzed to afford highly accurate molecular constants, including band origins, and rotational and spin-orbit constants. The spin-orbit coupling constants of the previously published lowest five levels are revised in sign and magnitude, requiring an overhaul of previously published molecular constants. The analysis is supported by high level ab initio calculations. Lifetimes of all observed levels were recorded and found to be in excellent agreement with ab initio predicted values up to v = 11. v = 12 was found to exhibit a much reduced lifetime and fluorescence quantum yield, which is attributed to the onset of predissociation. This brackets the dissociation energy of ground state XΣg+1 C ₂ between 6.1803 and 6.2553 eV, in agreement with the Active Thermochemical Tables.