Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy
Zero-field splitting (ZFS) parameters are fundamentally tied to the geometries of metal ion complexes. Despite their critical importance for understanding the magnetism and spectroscopy of metal complexes, they are not routinely available through general laboratory-based techniques, and are often in...
| Main Authors: | , , , , , , , , , |
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| Format: | Article |
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Royal Society of Chemistry (RSC)
2018
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| Online Access: | http://hdl.handle.net/1721.1/113263 https://orcid.org/0000-0002-7706-8121 https://orcid.org/0000-0003-2698-1655 https://orcid.org/0000-0003-1322-4786 https://orcid.org/0000-0002-7089-2724 https://orcid.org/0000-0002-0737-6786 https://orcid.org/0000-0002-1262-1264 https://orcid.org/0000-0002-6394-4987 https://orcid.org/0000-0001-7804-5418 |
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| author | Lu, Jian Ozel, Ilkem Ozge Belvin, Carina Aiello Li, Xian Skorupskii, Grigorii Sun, Lei Ofori-Okai, Benjamin Kwasi Dinca, Mircea Gedik, Nuh Nelson, Keith Adam |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Lu, Jian Ozel, Ilkem Ozge Belvin, Carina Aiello Li, Xian Skorupskii, Grigorii Sun, Lei Ofori-Okai, Benjamin Kwasi Dinca, Mircea Gedik, Nuh Nelson, Keith Adam |
| author_sort | Lu, Jian |
| collection | MIT |
| description | Zero-field splitting (ZFS) parameters are fundamentally tied to the geometries of metal ion complexes. Despite their critical importance for understanding the magnetism and spectroscopy of metal complexes, they are not routinely available through general laboratory-based techniques, and are often inferred from magnetism data. Here we demonstrate a simple tabletop experimental approach that enables direct and reliable determination of ZFS parameters in the terahertz (THz) regime. We report time-domain measurements of electron paramagnetic resonance (EPR) signals associated with THz-frequency ZFSs in molecular complexes containing high-spin transition-metal ions. We measure the temporal profiles of the free-induction decays of spin resonances in the complexes at zero and nonzero external magnetic fields, and we derive the EPR spectra via numerical Fourier transformation of the time-domain signals. In most cases, absolute values of the ZFS parameters are extracted from the measured zero-field EPR frequencies, and the signs can be determined by zero-field measurements at two different temperatures. Field-dependent EPR measurements further allow refined determination of the ZFS parameters and access to the g-factor. The results show good agreement with those obtained by other methods. The simplicity of the method portends wide applicability in chemistry, biology and material science. |
| first_indexed | 2024-09-23T15:42:48Z |
| format | Article |
| id | mit-1721.1/113263 |
| institution | Massachusetts Institute of Technology |
| last_indexed | 2024-09-23T15:42:48Z |
| publishDate | 2018 |
| publisher | Royal Society of Chemistry (RSC) |
| record_format | dspace |
| spelling | mit-1721.1/1132632022-09-29T15:39:45Z Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy Lu, Jian Ozel, Ilkem Ozge Belvin, Carina Aiello Li, Xian Skorupskii, Grigorii Sun, Lei Ofori-Okai, Benjamin Kwasi Dinca, Mircea Gedik, Nuh Nelson, Keith Adam Massachusetts Institute of Technology. Department of Chemistry Massachusetts Institute of Technology. Department of Physics Lu, Jian Ozel, Ilkem Ozge Belvin, Carina Aiello Li, Xian Skorupskii, Grigorii Sun, Lei Ofori-Okai, Benjamin Kwasi Dinca, Mircea Gedik, Nuh Nelson, Keith Adam Zero-field splitting (ZFS) parameters are fundamentally tied to the geometries of metal ion complexes. Despite their critical importance for understanding the magnetism and spectroscopy of metal complexes, they are not routinely available through general laboratory-based techniques, and are often inferred from magnetism data. Here we demonstrate a simple tabletop experimental approach that enables direct and reliable determination of ZFS parameters in the terahertz (THz) regime. We report time-domain measurements of electron paramagnetic resonance (EPR) signals associated with THz-frequency ZFSs in molecular complexes containing high-spin transition-metal ions. We measure the temporal profiles of the free-induction decays of spin resonances in the complexes at zero and nonzero external magnetic fields, and we derive the EPR spectra via numerical Fourier transformation of the time-domain signals. In most cases, absolute values of the ZFS parameters are extracted from the measured zero-field EPR frequencies, and the signs can be determined by zero-field measurements at two different temperatures. Field-dependent EPR measurements further allow refined determination of the ZFS parameters and access to the g-factor. The results show good agreement with those obtained by other methods. The simplicity of the method portends wide applicability in chemistry, biology and material science. United States. Office of Naval Research (Grant N00014-13-1-0509) National Science Foundation (U.S.) (Grant CHE-1111557) United States. Department of Energy. Office of Basic Energy Sciences (Award DE-FG02-08ER46521) National Science Foundation (U.S.) (Grant 1122374) 2018-01-22T20:24:03Z 2018-01-22T20:24:03Z 2017-04 2017-02 2018-01-19T18:46:58Z Article http://purl.org/eprint/type/JournalArticle 2041-6520 2041-6539 http://hdl.handle.net/1721.1/113263 Lu, Jian, et al. “Rapid and Precise Determination of Zero-Field Splittings by Terahertz Time-Domain Electron Paramagnetic Resonance Spectroscopy.” Chem. Sci. 8, 11 (April 2017): 7312–7323 © 2017 The Royal Society of Chemistry. https://orcid.org/0000-0002-7706-8121 https://orcid.org/0000-0003-2698-1655 https://orcid.org/0000-0003-1322-4786 https://orcid.org/0000-0002-7089-2724 https://orcid.org/0000-0002-0737-6786 https://orcid.org/0000-0002-1262-1264 https://orcid.org/0000-0002-6394-4987 https://orcid.org/0000-0001-7804-5418 http://dx.doi.org/10.1039/C7SC00830A Chemical Science Creative Commons Attribution 3.0 Unported license http://creativecommons.org/licenses/by/3.0/ application/pdf Royal Society of Chemistry (RSC) Royal Society of Chemistry |
| spellingShingle | Lu, Jian Ozel, Ilkem Ozge Belvin, Carina Aiello Li, Xian Skorupskii, Grigorii Sun, Lei Ofori-Okai, Benjamin Kwasi Dinca, Mircea Gedik, Nuh Nelson, Keith Adam Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy |
| title | Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy |
| title_full | Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy |
| title_fullStr | Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy |
| title_full_unstemmed | Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy |
| title_short | Rapid and precise determination of zero-field splittings by terahertz time-domain electron paramagnetic resonance spectroscopy |
| title_sort | rapid and precise determination of zero field splittings by terahertz time domain electron paramagnetic resonance spectroscopy |
| url | http://hdl.handle.net/1721.1/113263 https://orcid.org/0000-0002-7706-8121 https://orcid.org/0000-0003-2698-1655 https://orcid.org/0000-0003-1322-4786 https://orcid.org/0000-0002-7089-2724 https://orcid.org/0000-0002-0737-6786 https://orcid.org/0000-0002-1262-1264 https://orcid.org/0000-0002-6394-4987 https://orcid.org/0000-0001-7804-5418 |
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