Communication: New insight into the barrier governing CO2 formation from OH+CO

Despite its relative simplicity, the role of tunneling in the reaction OH + CO -> H + CO2 has eluded the quantitative predictive powers of theoretical reaction dynamics. In this study a one-dimensional effective barrier to the formation of H + CO2 from the HOCO intermediate is directly extracted from dissociative photodetachment experiments on HOCO and DOCO. Comparison of this barrier to a computed minimum-energy barrier shows that tunneling deviates significantly from the calculated minimum-energy pathway, predicting product internal energy distributions that match those found in the experiment and tunneling lifetimes short enough to contribute significantly to the overall reaction. This barrier can be of direct use in kinetic and statistical models and aid in the further refinement of the potential energy surface and reaction dynamics calculations for this system. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3589860]