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 journalArticlepeer-review

33 Citations (SciVal)


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 languageEnglish
Pages (from-to)825
Number of pages10
JournalNature Communications
Issue number1
Publication statusPublished - 11 Feb 2022
Externally publishedYes

Bibliographical note

Data availability
Raw research data files supporting this publication (including computational input/
output files, and raw spectral data) are available at

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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