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H/D isotope effect observed in the isotropic Fermi contact interaction of formyl radical: Experimental and theoretical analysis of the inter- and intra-molecular dynamics
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK). Nanjing Tech University, People’s Republic of China; Luleå University of Technology, Sweden; Petru Poni Institute of Macromolecular Chemistry, Romania.
Number of Authors: 32020 (English)In: AIP Advances, E-ISSN 2158-3226, Vol. 10, no 12, article id 125309Article in journal (Refereed) Published
Abstract [en]

An unexpected deficit of the computed hyper fine coupling constant in normal formyl HCO radicals, compared to that expected based on the proton to deuteron gyromagnetic ratio of the DCO species, was observed in experimental electron paramagnetic resonance studies of HCO and DCO radicals in a CO solid matrix at cryogenic conditions. Still, the matrix was found to have only a small effect on the anisotropic parts of the magnetic parameter tensors. The underlying isotope effect between the lighter proton and the heavier deuteron on the motional dynamics was verified and elucidated by quantum chemical calculations. The experimental results obtained within a temperature range of 1.4 K-4.2 K require special attention due to the tunneling motions of the molecule and its constituent particles. The effect from vibrational, rotational, and librational motion observed in the molecular states of formyl as a probe, averaged over the dynamics of the low temperature CO matrix isolation, reveals a clear proton isotope effect under both classical and quantum conditions.

Place, publisher, year, edition, pages
2020. Vol. 10, no 12, article id 125309
National Category
Physical Sciences
Identifiers
URN: urn:nbn:se:su:diva-189196DOI: 10.1063/5.0027835ISI: 000597318600002OAI: oai:DiVA.org:su-189196DiVA, id: diva2:1519440
Available from: 2021-01-18 Created: 2021-01-18 Last updated: 2023-03-28Bibliographically approved

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