Substituent effects on H3 + formation via H2 roaming mechanisms from organic molecules under strong-field photodissociation.

Abstract

Roaming chemical reactions are often associated with neutral molecules. The recent findings of roaming processes in ionic species, in particular, ones that lead to the formation of H3 + under strong-field laser excitation, are of considerable interest. Given that such gas-phase reactions are initiated by double ionization and subsequently facilitated through deprotonation, we investigate the strong-field photodissociation of ethanethiol, also known as ethyl mercaptan, and compare it to results from ethanol. Contrary to expectations, the H3 + yield was found to be an order of magnitude lower for ethanethiol at certain laser field intensities, despite its lower ionization energy and higher acidity compared to ethanol. In-depth analysis of the femtosecond time-resolved experimental findings, supported by ab initio quantum mechanical calculations, provides key information regarding the roaming mechanisms related to H3 + formation. Results of this study on the dynamics of dissociative half-collisions involving H3 +, a vital cation which acts as a Brønsted-Lowry acid protonating interstellar organic compounds, may also provide valuable information regarding the formation mechanisms and observed natural abundances of complex organic molecules in interstellar media and planetary atmospheres.