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Electronic Rearrangements and Angular Momentum Couplings in Quantum State-to-State Channels of Prototype Oxidation Processes

[Image: see text] An innovative theoretical method to describe the microscopic dynamics of chemi-ionization reactions as prototype oxidation processes driven by selective electronic rearrangements has been recently published. It was developed and applied to reactions of Ne* atoms excited in their me...

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Detalles Bibliográficos
Autores principales: Falcinelli, Stefano, Vecchiocattivi, Franco, Pirani, Fernando
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8023699/
https://www.ncbi.nlm.nih.gov/pubmed/33593059
http://dx.doi.org/10.1021/acs.jpca.0c09701
Descripción
Sumario:[Image: see text] An innovative theoretical method to describe the microscopic dynamics of chemi-ionization reactions as prototype oxidation processes driven by selective electronic rearrangements has been recently published. It was developed and applied to reactions of Ne* atoms excited in their metastable (3)P(J) state, and here, its physical background is extensively described in order to provide a clear description of the microscopic phenomenon underlying the chemical reactivity of the oxidative processes under study. It overcomes theoretical models previously proposed and reproduces experimental results obtained in different laboratories. Two basic reaction mechanisms have been identified: (i) at low collision energies, a weakly bounded transition state is formed which spontaneously ionizes through a radiative physical mechanism (photoionization); (ii) in the hyperthermal regime, an elementary oxidation process occurs. In this paper, the selectivity of the electronic rearrangements triggering the two mechanisms has been related to the angular momentum couplings by Hund’s cases, casting further light on fundamental aspects of the reaction stereodynamics of general interest. The obtained results allow peculiar characteristics and differences of the terrestrial oxidizing chemistry compared to that of astrochemical environments to be highlighted.