title: Stereoselectivity in Autoionization Reactions of Hydrogenated Molecules by Metastable Noble Gas Atoms: The Role of Electronic Couplings.
abstract: Focus in the present paper is on the analysis of total and partial ionization cross sections, measured in absolute value as a function of the collision energy, representative of the probability of ionic product formation in selected electronic states in Ne*-H2 O, H2 S, and NH3 collisions. In order to characterize the imaginary part of the optical potential, related to electronic couplings, we generalize a methodology to obtain direct information on the opacity function of these reactions. Such a methodology has been recently exploited to test the real part of the optical potential (S. Falcinelli et al., Chem. Eur. J., 2016, 22, 764-771). Depending on the balance of noncovalent contributions, the real part controls the approach of neutral reactants, the removal of ionic products, and the structure of the transition state. Strength, range, and stereoselectivity of electronic couplings, triggering these and many other reactions, are directly obtained from the present investigation.
authors.affiliation: Department of Civil and Environmental Engineering, University of Perugia, Via G. Duranti 93, 06125, Perugia, Italy. stefano.falcinelli@unipg.it.
authors.forename: Stefano
authors.identifier: http://orcid.org/0000-0002-5301-6730
authors.initials: S
authors.lastname: Falcinelli
authors.affiliation: Department of Civil and Environmental Engineering, University of Perugia, Via G. Duranti 93, 06125, Perugia, Italy.
authors.forename: Marzio
authors.initials: M
authors.lastname: Rosi
authors.affiliation: Department of Chemistry, Biology and Biotechnology, University of Perugia, Via Elce di Sotto 8, 06123, Perugia, Italy.
authors.forename: Simonetta
authors.initials: S
authors.lastname: Cavalli
authors.affiliation: Department of Chemistry, Biology and Biotechnology, University of Perugia, Via Elce di Sotto 8, 06123, Perugia, Italy.
authors.forename: Fernando
authors.initials: F
authors.lastname: Pirani
authors.affiliation: Department of Civil and Environmental Engineering, University of Perugia, Via G. Duranti 93, 06125, Perugia, Italy.
authors.forename: Franco
authors.initials: F
authors.lastname: Vecchiocattivi
keywords: collisional autoionization; electron transfer; optical potential; penning ionization; semiclassical