Site-specific hydrogen-atom elimination in photoexcited ethyl radical

The photochemistry of the ethyl radical following excitation to the 3p Rydberg state is investigated in a joint experimental and theoretical study. Velocity map images for hydrogen atoms detected from photoexcited isotopologues CH(3)CH(2), CH(3)CD(2) and CD(3)CH(2) at ∼201 nm, are discussed along with high-level ab initio electronic structure calculations of potential energy curves and non-adiabatic coupling matrix elements (NACME). A novel mechanism governed by a conical intersection allowing prompt site-specific hydrogen-atom elimination is presented and discussed. For this mechanism to occur, an initial ro-vibrational excitation is allocated to the radical permitting to access this reaction pathway and thus to control the ethyl photochemistry. While hydrogen-atom elimination from cold ethyl radicals occurs through internal conversion into lower electronic states followed by slow statistical dissociation, prompt site-specific C(α) elimination into CH(3)CH + H, occurring through a fast non-adiabatic crossing to a valence bound state followed by dissociation through a conical intersection, is accessed by means of an initial ro-vibrational energy content into the radical. The role of a particularly effective vibrational promoting mode in this prompt photochemical reaction pathway is discussed.