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The role of the multiconfigurational character of nitronyl-nitroxide in the singlet-triplet energy gap of its diradicals

Abstract

While technological applications demand for the setup of reliable computational techniques and accurate experiments for the characterization of diradicals, these species are still challenging systems for both theory and experiments. The singlet-triplet energy gap, the J-term of the Heisenberg-Dirac-vanVleck spin Hamiltonian, is the most significant quantity, whose measurement and computational evaluation may serve for understanding and governing magnetism at the molecular scale. In this framework, we report here on a study of three diradicals containing one or two nitronyl-nitroxide species. Using Difference Dedicated Configuration Interaction (DDCI) calculations we investigate on the multiconfigurational character of the O-N-C-N-O fragment of this unit. We find that only through a computational scheme that takes this nature into account, we can be confident of obtaining reliable values of the spin-spin coupling J. In addition, we show that the reduced DDCI2 scheme with a CAS(2,2) reference, apparently able in some cases to reproduce experimental data, provides quite poor results in the present context.

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Publication details

The article was received on 05 Apr 2018, accepted on 14 Jun 2018 and first published on 14 Jun 2018


Article type: Paper
DOI: 10.1039/C8CP02165A
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
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    The role of the multiconfigurational character of nitronyl-nitroxide in the singlet-triplet energy gap of its diradicals

    V. Barone, I. CACELLI and A. Ferretti, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C8CP02165A

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