Spectroscopy and dynamics of the HOCO radical: insights into the OH + CO → H + CO2 reaction

Phys Chem Chem Phys. 2014 Sep 28;16(36):19091-105. doi: 10.1039/c4cp02593h.


After more than forty years of scrutiny, crucial new details regarding the elementary reaction OH + CO → H + CO2 are still emerging from experimental and theoretical studies of the HOCO radical intermediate. In this perspective, previous studies of this elementary reaction and the structure and energetics of the HOCO radical will be briefly reviewed. Particular attention will be paid to the experimental techniques used in our laboratory to prepare excited HOCO radicals by both photodetachment and dissociative photodetachment of HOCO(-). These experiments directly probe the dynamics occurring on the ground and excited states of the HOCO radical, and are sensitive to both direct and tunneling-induced dissociation. Photoelectron-photofragment coincidence experiments on HOCO(-) in particular have been used to study tunneling from the HOCO well to form H + CO2 products. In addition, new experimental insights into the OH + CO entrance channel for the reaction will be presented. These studies have provided a number of constraints on the potential energy surface for this system from an energetic and dynamical perspective, and have helped spur a renewed effort to characterize the global potential energy surface and reaction dynamics of this fundamental chemical reaction. Outstanding questions and new directions for future work on the HOCO radical will be discussed.