Exploring the Vibrational Side of Spin-Phonon Coupling in Single-Molecule Magnets via 161 Dy Nuclear Resonance Vibrational Spectroscopy

Lena Scherthan; Rouven F Pfleger; Hendrik Auerbach; Tim Hochdörffer; Juliusz A Wolny; Wenli Bi; Jiyong Zhao; Michael Y Hu; E Ercan Alp; Christopher E Anson; Rolf Diller; Annie K Powell; Volker Schünemann

doi:10.1002/anie.201914728

Exploring the Vibrational Side of Spin-Phonon Coupling in Single-Molecule Magnets via ¹⁶¹ Dy Nuclear Resonance Vibrational Spectroscopy

Angew Chem Int Ed Engl. 2020 Jun 2;59(23):8818-8822. doi: 10.1002/anie.201914728. Epub 2020 Apr 24.

Authors

Affiliations

¹ Department of Physics, Technische Universität Kaiserslautern, Erwin-Schrödinger-Str. 46, 67663, Kaiserslautern, Germany.
² Institute of Inorganic Chemistry, Karlsruhe Institute of Technology, Engesserstr. 15, 76131, Karlsruhe, Germany.
³ Advanced Photon Source, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL, 60439, USA.
⁴ Department of Physics, University of Alabama at Birmingham, Birmingham, AL, 35294, USA.
⁵ Institute of Nanotechnology, Karlsruhe Institute of Technology, 76021, Karlsruhe, Germany.

Abstract

Synchrotron-based nuclear resonance vibrational spectroscopy (NRVS) using the Mössbauer isotope ¹⁶¹ Dy has been employed for the first time to study the vibrational properties of a single-molecule magnet (SMM) incorporating Dy^III , namely [Dy(Cy₃ PO)₂ (H₂ O)₅ ]Br₃ ⋅2 (Cy₃ PO)⋅2 H₂ O ⋅2 EtOH. The experimental partial phonon density of states (pDOS), which includes all vibrational modes involving a displacement of the Dy^III ion, was reproduced by means of simulations using density functional theory (DFT), enabling the assignment of all intramolecular vibrational modes. This study proves that ¹⁶¹ Dy NRVS is a powerful experimental tool with significant potential to help to clarify the role of phonons in SMMs.

Keywords: dysprosium; nuclear resonance vibrational spectroscopy; phonons; single-molecule magnets.

Abstract

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