journal article·2020-12-01Open access

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

Yurij A. Dmitriev, Aatto Laaksonen, Nikolas P. Benetis

AIP Advances· Volume 10· Issue 12

Abstract

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.
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Research context

OpenAlex topics: Advanced Chemical Physics Studies · Quantum, superfluid, helium dynamics · Molecular Spectroscopy and Structure

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Ioffe Institute 1 , 26 Politekhnicheskaya Street, 194021 St Petersburg, Russia

State Key Laboratory of Material-Oriented Chemical Engineering, Nanjing Tech University 2 , Nanjing 210009, People’s Republic of China

Energy Engineering, Division of Energy Science, Luleå University of Technology 3 , Luleå 971 87, Sweden

Centre of Advanced Research in Bionanoconjugates and Biopolymers, Petru Poni Institute of Macromolecular Chemistry 4 , Aleea Grigore Ghica-Voda, 41A, 700487 Iasi, Romania

Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University 5 , SE-106 91 Stockholm, Sweden

Department of Chemical Engineering, University of Western Macedonia 6 , Kila Kozani 501 00, Greece

Funding

EC Research Innovation Action under H2020 Program, Project HPC-EUROPA3 · Ministry of Research and Innovation of Romania, within PNCDI III · Swedish Research Council · PDC in KTH · Swedish National Infrastructure for Computing at PDC

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