Chemistry Publications and Other Works

Source Publication (e.g., journal title)

Nature Communications

Document Type

Article

Publication Date

7-3-2018

DOI

10.1038/s41467-018-04896-0

Abstract

Spin–phonon coupling plays an important role in single-molecule magnets and molecular qubits. However, there have been few detailed studies of its nature. Here, we show for the first time distinct couplings of g phonons of CoII(acac)2(H2O)2 (acac = acetylacetonate) and its deuterated analogs with zero-field-split, excited magnetic/spin levels (Kramers doublet (KD)) of the S = 3/2 electronic ground state. The couplings are observed as avoided crossings in magnetic-field-dependent Raman spectra with coupling constants of 1–2 cm−1. Far-IR spectra reveal the magnetic-dipole-allowed, inter-KD transition, shifting to higher energy with increasing field. Density functional theory calculations are used to rationalize energies and symmetries of the phonons. A vibronic coupling model, supported by electronic structure calculations, is proposed to rationalize the behavior of the coupled Raman peaks. This work spectroscopically reveals and quantitates the spin–phonon couplings in typical transition metal complexes and sheds light on the origin of the spin–phonon entanglement.

Comments

This article was published openly thanks to the University of Tennessee Open Publishing Support Fund.

Licensed under a Creative Commons Attribution 4.0 International license.

Submission Type

Publisher's Version

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