Site-specific hydrogen-atom elimination in photoexcited ethyl radical.

ABSTRACT: 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 CH₃CH₂, CH₃CD₂ and CD₃CH₂ 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 ethy

SUBMITTER: Chicharro DV 

PROVIDER: S-EPMC6610558 | biostudies-literature | 2019 Jul

REPOSITORIES: biostudies-literature