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Vibronic Coupling in a Molecular 4f Qubit

preprint
submitted on 06.02.2021, 14:40 and posted on 08.02.2021, 10:05 by Jonathan Marbey, Jon G. C. Kragskow, Christian Dirk Buch, Joscha Nehrkorn, Mykhaylo Ozerov, Stergios Piligkos, Stephen Hill, Nicholas Chilton

Vibronic coupling, the interaction between molecular vibrations and electronic states, is a pervasive 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 probe vibronic transitions in a YbIII molecular qubit directly. We find intense signals near electronic states, which we show arise due to an “envelope effect” in the vibronic coupling Hamiltonian, and we calculate the vibronic coupling 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 C3 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.

History

Email Address of Submitting Author

nicholas.chilton@manchester.ac.uk

Institution

The University of Manchester

Country

United Kingdom

ORCID For Submitting Author

0000-0002-8604-0171

Declaration of Conflict of Interest

No conflict of interest

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