Publication details

Quadratic Spin–Orbit Mechanism of the Electronic g-Tensor

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Year of publication 2023
Type Article in Periodical
Magazine / Source Journal of Chemical Theory and Computation
MU Faculty or unit

Central European Institute of Technology

Web DOI: 10.1021/acs.jctc.2c01213
Keywords Electron paramagnetic resonance; g tensor; spin-orbit coupling; MO theory
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Description Understanding how the electronic g-tensor is linked to the electronic structure is desirable for the correct interpretation of electron paramagnetic resonance spectra. For heavy-element compounds with large spin–orbit (SO) effects, this is still not completely clear. We report our investigation of quadratic SO contributions to the g-shift in heavy transition metal complexes. We implemented third-order perturbation theory in order to analyze the contributions arising from frontier molecular spin orbitals (MSOs). We show that the dominant quadratic SO term¦spin-Zeeman (SO2/SZ)¦generally makes a negative contribution to the g-shift, irrespective of the particular electronic configuration or molecular symmetry. We further analyze how the SO2/SZ contribution adds to or subtracts from the linear orbital-Zeeman (SO/OZ) contribution to the individual principal components of the g-tensor. Our study suggests that the SO2/SZ mechanism decreases the anisotropy of the g-tensor in early transition metal complexes and increases it in late transition metal complexes. Finally, we apply MSO analysis to the investigation of g-tensor trends in a set of closely related Ir and Rh pincer complexes and evaluate the influence of different chemical factors (the nuclear charge of the central atom and the terminal ligand) on the magnitudes of the g-shifts. We expect our conclusions to aid the understanding of spectra in magnetic resonance investigations of heavy transition metal compounds.
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