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Spin-spin relaxation of nuclear quadrupole resonance coherences and the important role of degenerate energy levels
Umeå University, Faculty of Science and Technology, Department of Chemistry.ORCID iD: 0000-0002-9277-4534
2020 (English)In: Molecular Physics, ISSN 0026-8976, E-ISSN 1362-3028, Vol. 118, no 17, article id e1743888Article in journal (Refereed) Published
Abstract [en]

We present an extension of a Redfield approach for calculating spin-spin relaxation rates of zero-field nuclear quadrupole resonance (NQR) coherences, which was published in [Kruk et al., PCCP, 2018, 20, 23414-23426]. The oversimplification of the secular approximation made in the recent paper makes the calculation invalid for zero-field NQR and has led to partially large deviations between predicted and experimental data from 209Bi-containing molecular crystals. Furthermore, these deviations led to speculations about an additional dipole-dipole relaxation mechanism besides the main electric field gradient (EFG) fluctuations. Here, we demonstrate how a complete application of the Redfield relaxation expression eliminates the deviation from experimental data without the need for additional assumptions. In particular, we point out the important role of off-diagonal elements in the Redfield relaxation matrix within the 3/2-1/2 block appearing due to degenerate energy levels. The resulting coupling between single and double coherence spin density elements leads to a faster coherence decay than for all other transitions. The pseudo rotational model for EFG fluctuations, as proposed in the earlier publication and usually applied for isotropic liquids, is extended in a second analysis by introducing a vibrational mode to account for the case of crystalline solids.

Place, publisher, year, edition, pages
Taylor & Francis, 2020. Vol. 118, no 17, article id e1743888
Keywords [en]
Nuclear quadrupole resonance, spin-spin relaxation, Bloch-Wangsness-Redfield theory, EFG fluctuations, molecular crystals
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:umu:diva-174277DOI: 10.1080/00268976.2020.1743888ISI: 000526479500001Scopus ID: 2-s2.0-85083851731OAI: oai:DiVA.org:umu-174277DiVA, id: diva2:1459760
Funder
EU, European Research Council, 665172Available from: 2020-08-20 Created: 2020-08-20 Last updated: 2021-01-12Bibliographically approved

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Westlund, Per-Olof

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