Issue 26, 2019

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 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 Cα elimination into CH3CH + 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.

Graphical abstract: Site-specific hydrogen-atom elimination in photoexcited ethyl radical

Supplementary files

Article information

Article type
Edge Article
Submitted
02 May 2019
Accepted
22 May 2019
First published
22 May 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2019,10, 6494-6502

Site-specific hydrogen-atom elimination in photoexcited ethyl radical

D. V. Chicharro, S. M. Poullain, A. Zanchet, A. Bouallagui, A. García-Vela, M. L. Senent, L. Rubio-Lago and L. Bañares, Chem. Sci., 2019, 10, 6494 DOI: 10.1039/C9SC02140J

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