Analysis of vibronic coupling in a 4f molecular magnet with FIRMS

Jon G C Kragskow; Jonathan Marbey; Christian D Buch; Joscha Nehrkorn; Mykhaylo Ozerov; Stergios Piligkos; Stephen Hill; Nicholas F Chilton

doi:10.1038/s41467-022-28352-2

Analysis of vibronic coupling in a 4f molecular magnet with FIRMS

Jon G C Kragskow, Jonathan Marbey, Christian D Buch, Joscha Nehrkorn, Mykhaylo Ozerov, Stergios Piligkos, Stephen Hill, Nicholas F Chilton

Research output: Contribution to journal › Article › peer-review

47 Citations (SciVal)

Abstract

Vibronic coupling, the interaction between molecular vibrations and electronic states, is a fundamental effect that profoundly affects chemical processes. In the case of molecular magnetic materials, vibronic, or spin-phonon, coupling leads to magnetic relaxation, which equates to loss of magnetic memory and loss of phase coherence in molecular magnets and qubits, respectively. The study of vibronic coupling is challenging, and most experimental evidence is indirect. Here we employ far-infrared magnetospectroscopy to directly probe vibronic transitions in [Yb(trensal)] (where H 3trensal = 2,2,2-tris(salicylideneimino)trimethylamine). We find intense signals near electronic states, which we show arise due to an "envelope effect" in the vibronic coupling Hamiltonian, which we calculate fully ab initio to simulate the spectra. We subsequently show that vibronic coupling is strongest for vibrational modes that simultaneously distort the first coordination sphere and break the C 3 symmetry of the molecule. With this knowledge, vibrational modes could be identified and engineered to shift their energy towards or away from particular electronic states to alter their impact. Hence, these findings provide new insights towards developing general guidelines for the control of vibronic coupling in molecules.

Original language	English
Pages (from-to)	825
Number of pages	10
Journal	Nature Communications
Volume	13
Issue number	1
DOIs	https://doi.org/10.1038/s41467-022-28352-2
Publication status	Published - 11 Feb 2022
Externally published	Yes

Bibliographical note

Data availability
Raw research data files supporting this publication (including computational input/
output files, and raw spectral data) are available at https://doi.org/10.48420/16698526.

We thank The University of Manchester for access to the Computational Shared Facility, the EPSRC (studentship to J.G.C.K.), and The Royal Society (University Research Fellowship to N.F.C.). This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 851504 to N.F.C.) and the US Department of Energy (under DE-SC0020260 to S.H.). A portion of this work was performed at the NHMFL which is supported by the US National Science Foundation (grant number DMR-1644779) and the State of Florida. S.P. thanks the VILLUM FONDEN for research grant 13376. We thank Prof. Richard Winpenny, Prof. Eric McInnes, Prof. David Collison and Prof. David Mills for insightful comments.

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Cite this

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title = "Analysis of vibronic coupling in a 4f molecular magnet with FIRMS",

abstract = "Vibronic coupling, the interaction between molecular vibrations and electronic states, is a fundamental effect that profoundly affects chemical processes. In the case of molecular magnetic materials, vibronic, or spin-phonon, coupling leads to magnetic relaxation, which equates to loss of magnetic memory and loss of phase coherence in molecular magnets and qubits, respectively. The study of vibronic coupling is challenging, and most experimental evidence is indirect. Here we employ far-infrared magnetospectroscopy to directly probe vibronic transitions in [Yb(trensal)] (where H 3trensal = 2,2,2-tris(salicylideneimino)trimethylamine). We find intense signals near electronic states, which we show arise due to an {"}envelope effect{"} in the vibronic coupling Hamiltonian, which we calculate fully ab initio to simulate the spectra. We subsequently show that vibronic coupling is strongest for vibrational modes that simultaneously distort the first coordination sphere and break the C 3 symmetry of the molecule. With this knowledge, vibrational modes could be identified and engineered to shift their energy towards or away from particular electronic states to alter their impact. Hence, these findings provide new insights towards developing general guidelines for the control of vibronic coupling in molecules. ",

author = "Kragskow, {Jon G C} and Jonathan Marbey and Buch, {Christian D} and Joscha Nehrkorn and Mykhaylo Ozerov and Stergios Piligkos and Stephen Hill and Chilton, {Nicholas F}",

note = "Data availability Raw research data files supporting this publication (including computational input/ output files, and raw spectral data) are available at https://doi.org/10.48420/16698526. We thank The University of Manchester for access to the Computational Shared Facility, the EPSRC (studentship to J.G.C.K.), and The Royal Society (University Research Fellowship to N.F.C.). This project has received funding from the European Research Council (ERC) under the European Union{\textquoteright}s Horizon 2020 research and innovation programme (grant agreement No. 851504 to N.F.C.) and the US Department of Energy (under DE-SC0020260 to S.H.). A portion of this work was performed at the NHMFL which is supported by the US National Science Foundation (grant number DMR-1644779) and the State of Florida. S.P. thanks the VILLUM FONDEN for research grant 13376. We thank Prof. Richard Winpenny, Prof. Eric McInnes, Prof. David Collison and Prof. David Mills for insightful comments.",

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T1 - Analysis of vibronic coupling in a 4f molecular magnet with FIRMS

AU - Kragskow, Jon G C

AU - Marbey, Jonathan

AU - Buch, Christian D

AU - Nehrkorn, Joscha

AU - Ozerov, Mykhaylo

AU - Piligkos, Stergios

AU - Hill, Stephen

AU - Chilton, Nicholas F

N1 - Data availability Raw research data files supporting this publication (including computational input/ output files, and raw spectral data) are available at https://doi.org/10.48420/16698526. We thank The University of Manchester for access to the Computational Shared Facility, the EPSRC (studentship to J.G.C.K.), and The Royal Society (University Research Fellowship to N.F.C.). This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 851504 to N.F.C.) and the US Department of Energy (under DE-SC0020260 to S.H.). A portion of this work was performed at the NHMFL which is supported by the US National Science Foundation (grant number DMR-1644779) and the State of Florida. S.P. thanks the VILLUM FONDEN for research grant 13376. We thank Prof. Richard Winpenny, Prof. Eric McInnes, Prof. David Collison and Prof. David Mills for insightful comments.

PY - 2022/2/11

Y1 - 2022/2/11

N2 - Vibronic coupling, the interaction between molecular vibrations and electronic states, is a fundamental effect that profoundly affects chemical processes. In the case of molecular magnetic materials, vibronic, or spin-phonon, coupling leads to magnetic relaxation, which equates to loss of magnetic memory and loss of phase coherence in molecular magnets and qubits, respectively. The study of vibronic coupling is challenging, and most experimental evidence is indirect. Here we employ far-infrared magnetospectroscopy to directly probe vibronic transitions in [Yb(trensal)] (where H 3trensal = 2,2,2-tris(salicylideneimino)trimethylamine). We find intense signals near electronic states, which we show arise due to an "envelope effect" in the vibronic coupling Hamiltonian, which we calculate fully ab initio to simulate the spectra. We subsequently show that vibronic coupling is strongest for vibrational modes that simultaneously distort the first coordination sphere and break the C 3 symmetry of the molecule. With this knowledge, vibrational modes could be identified and engineered to shift their energy towards or away from particular electronic states to alter their impact. Hence, these findings provide new insights towards developing general guidelines for the control of vibronic coupling in molecules.

AB - Vibronic coupling, the interaction between molecular vibrations and electronic states, is a fundamental effect that profoundly affects chemical processes. In the case of molecular magnetic materials, vibronic, or spin-phonon, coupling leads to magnetic relaxation, which equates to loss of magnetic memory and loss of phase coherence in molecular magnets and qubits, respectively. The study of vibronic coupling is challenging, and most experimental evidence is indirect. Here we employ far-infrared magnetospectroscopy to directly probe vibronic transitions in [Yb(trensal)] (where H 3trensal = 2,2,2-tris(salicylideneimino)trimethylamine). We find intense signals near electronic states, which we show arise due to an "envelope effect" in the vibronic coupling Hamiltonian, which we calculate fully ab initio to simulate the spectra. We subsequently show that vibronic coupling is strongest for vibrational modes that simultaneously distort the first coordination sphere and break the C 3 symmetry of the molecule. With this knowledge, vibrational modes could be identified and engineered to shift their energy towards or away from particular electronic states to alter their impact. Hence, these findings provide new insights towards developing general guidelines for the control of vibronic coupling in molecules.

UR - https://chemrxiv.org/engage/chemrxiv/article-details/61b3baf6d10aa5236d0bb047

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DO - 10.1038/s41467-022-28352-2

M3 - Article

C2 - 35149674

SN - 2041-1723

VL - 13

SP - 825

JO - Nature Communications

JF - Nature Communications

IS - 1

ER -

Analysis of vibronic coupling in a 4f molecular magnet with FIRMS

Abstract

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