Exploring the Vibrational Side of Spin-Phonon Coupling in Single-Molecule Magnets via 161Dy Nuclear Resonance Vibrational Spectroscopy
Abstract
Synchrotron-based nuclear resonance vibrational spectroscopy (NRVS) using the Mossbauer isotope 161Dy has been employed for the first time to study the vibrational properties of a single-molecule magnet (SMM) incorporating DyIII, namely [Dy(Cy3PO)(2)(H2O)(5)]Br-3•2 (Cy3PO)•2 H2O•2 EtOH. The experimental partial phonon density of states (pDOS), which includes all vibrational modes involving a displacement of the DyIII ion, was reproduced by means of simulations using density functional theory (DFT), enabling the assignment of all intramolecular vibrational modes. This study proves that 161Dy NRVS is a powerful experimental tool with significant potential to help to clarify the role of phonons in SMMs.
- Authors:
-
[1];
[2];
[1];
[5];
[1]
- Department of PhysicsTechnische Universität Kaiserslautern Erwin-Schrödinger-Str. 46 67663 Kaiserslautern Germany
- Institute of Inorganic ChemistryKarlsruhe Institute of Technology Engesserstr. 15 76131 Karlsruhe Germany
- Advanced Photon SourceArgonne National Laboratory 9700 South Cass Avenue Argonne IL 60439 USA, Department of PhysicsUniversity of Alabama at Birmingham Birmingham AL 35294 USA
- Advanced Photon SourceArgonne National Laboratory 9700 South Cass Avenue Argonne IL 60439 USA
- Institute of Inorganic ChemistryKarlsruhe Institute of Technology Engesserstr. 15 76131 Karlsruhe Germany, Institute of NanotechnologyKarlsruhe Institute of Technology 76021 Karlsruhe Germany
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); German Research Foundation (DFG); Consortium for Materials Properties Research in Earth Sciences (COMPRES); National Science Foundation (NSF)
- OSTI Identifier:
- 1616193
- Alternate Identifier(s):
- OSTI ID: 1616195; OSTI ID: 1631809
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Published Article
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition) Journal Volume: 59 Journal Issue: 23; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- Germany
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; dysprosium; nuclear resonance vibrational spectroscopy; phonons; single-molecule magnets
Citation Formats
Scherthan, Lena, Pfleger, Rouven F., Auerbach, Hendrik, Hochdörffer, Tim, Wolny, Juliusz A., Bi, Wenli, Zhao, Jiyong, Hu, Michael Y., Alp, E. Ercan, Anson, Christopher E., Diller, Rolf, Powell, Annie K., and Schünemann, Volker. Exploring the Vibrational Side of Spin-Phonon Coupling in Single-Molecule Magnets via 161Dy Nuclear Resonance Vibrational Spectroscopy. Germany: N. p., 2020.
Web. doi:10.1002/anie.201914728.
Scherthan, Lena, Pfleger, Rouven F., Auerbach, Hendrik, Hochdörffer, Tim, Wolny, Juliusz A., Bi, Wenli, Zhao, Jiyong, Hu, Michael Y., Alp, E. Ercan, Anson, Christopher E., Diller, Rolf, Powell, Annie K., & Schünemann, Volker. Exploring the Vibrational Side of Spin-Phonon Coupling in Single-Molecule Magnets via 161Dy Nuclear Resonance Vibrational Spectroscopy. Germany. https://doi.org/10.1002/anie.201914728
Scherthan, Lena, Pfleger, Rouven F., Auerbach, Hendrik, Hochdörffer, Tim, Wolny, Juliusz A., Bi, Wenli, Zhao, Jiyong, Hu, Michael Y., Alp, E. Ercan, Anson, Christopher E., Diller, Rolf, Powell, Annie K., and Schünemann, Volker. Tue .
"Exploring the Vibrational Side of Spin-Phonon Coupling in Single-Molecule Magnets via 161Dy Nuclear Resonance Vibrational Spectroscopy". Germany. https://doi.org/10.1002/anie.201914728.
@article{osti_1616193,
title = {Exploring the Vibrational Side of Spin-Phonon Coupling in Single-Molecule Magnets via 161Dy Nuclear Resonance Vibrational Spectroscopy},
author = {Scherthan, Lena and Pfleger, Rouven F. and Auerbach, Hendrik and Hochdörffer, Tim and Wolny, Juliusz A. and Bi, Wenli and Zhao, Jiyong and Hu, Michael Y. and Alp, E. Ercan and Anson, Christopher E. and Diller, Rolf and Powell, Annie K. and Schünemann, Volker},
abstractNote = {Synchrotron-based nuclear resonance vibrational spectroscopy (NRVS) using the Mossbauer isotope 161Dy has been employed for the first time to study the vibrational properties of a single-molecule magnet (SMM) incorporating DyIII, namely [Dy(Cy3PO)(2)(H2O)(5)]Br-3•2 (Cy3PO)•2 H2O•2 EtOH. The experimental partial phonon density of states (pDOS), which includes all vibrational modes involving a displacement of the DyIII ion, was reproduced by means of simulations using density functional theory (DFT), enabling the assignment of all intramolecular vibrational modes. This study proves that 161Dy NRVS is a powerful experimental tool with significant potential to help to clarify the role of phonons in SMMs.},
doi = {10.1002/anie.201914728},
journal = {Angewandte Chemie (International Edition)},
number = 23,
volume = 59,
place = {Germany},
year = {Tue Mar 17 00:00:00 EDT 2020},
month = {Tue Mar 17 00:00:00 EDT 2020}
}
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Figures / Tables:
Figure 1: Molecular structure of complex 1 (redrawn from coordinates in ref. [15] cyclohexyl H atoms omitted for clarity). Dy: purple, O: red, P: pink, C: gray, H: white.
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