Organic Mixed-Valence Compounds and the Overhauser Effect in Insulating Solids
Pylaeva S, Marx P, Singh G, Kühne TD, Roemelt M, Elgabarty H (2021)
Publication Type: Journal article
Publication year: 2021
Journal
Book Volume: 125
Pages Range: 867-874
Journal Issue: 3
Abstract
Recent experiments have shown that the organic free radical 1,3-bisdiphenylene-2-phenylallyl (BDPA) can induce an Overhauser effect dynamic nuclear polarization in insulating solids, a feat previously considered not to be possible. Here, we establish that this peculiar ability of the BDPA radical stems from its mixed-valence nature and the ensuing intramolecular charge transfer. Using state-of-the-art DMRGSCF calculations, we confirm the class II mixed-valence nature of BDPA with the characteristic double-well potential energy surface, and we investigate the mechanism of the consequent electron hopping. A two-component vibronic Hamiltonian is then employed to compute the rate of electron hopping from a quantum dynamical time-propagation of the density matrix. The predicted hyperfine coupling oscillations indeed fall within the frequency range required for an Overhauser effect. The paradigm of mixed-valence compounds as a mining source opens many possibilities for the development and fine tuning of novel polarizing agents.
Involved external institutions
Germany (DE)How to cite
APA:
Pylaeva, S., Marx, P., Singh, G., Kühne, T.D., Roemelt, M., & Elgabarty, H. (2021). Organic Mixed-Valence Compounds and the Overhauser Effect in Insulating Solids. Journal of Physical Chemistry A, 125(3), 867-874. https://doi.org/10.1021/acs.jpca.0c11296
MLA:
Pylaeva, Svetlana, et al. "Organic Mixed-Valence Compounds and the Overhauser Effect in Insulating Solids." Journal of Physical Chemistry A 125.3 (2021): 867-874.
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