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Interpretation of Exchange Interaction through Orbital Entanglement
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SYSNO ASEP 0540524 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Interpretation of Exchange Interaction through Orbital Entanglement Author(s) Chalupský, Jakub (UOCHB-X) RID, ORCID
Srnec, Martin (UFCH-W) RID, ORCID
Yanai, T. (JP)Source Title Journal of Physical Chemistry Letters. - : American Chemical Society - ISSN 1948-7185
Roč. 12, č. 4 (2021), s. 1268-1274Number of pages 7 s. Language eng - English Country US - United States Keywords exchange coupling ; magnetism ; orbital entanglement ; multireference calculations OECD category Physical chemistry R&D Projects GJ20-06451Y GA ČR - Czech Science Foundation (CSF) GA18-13093S GA ČR - Czech Science Foundation (CSF) LTAUSA19148 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) Method of publishing Limited access Institutional support UOCHB-X - RVO:61388963 ; UFCH-W - RVO:61388955 UT WOS 000618526700025 EID SCOPUS 85100710037 DOI 10.1021/acs.jpclett.0c03652 Annotation Recently, the analysis of single-orbital entropy and mutual information has been introduced as a tool for the investigation of contributions to the exchange (J) coupling between open-shell metal ions [Stein et al. J. Phys. Chem. Lett. 2019, 10, 6762-6770]. Here, we show that this analysis may lead to an incorrect interpretation of the J-coupling mechanism. Instead, we propose an orbital-entanglement analysis that is based on the two-electron density and that provides a coherent picture of the contributing exchange pathways, which seems fully consistent with the available J values. For this purpose, we used a prototypical bis-μ-oxo binuclear manganese complex ([Mn2O2(NH3)8]4+) and demonstrated that its antiferromagnetism (J < 0), calculated by using the active space composed of all valence pO and dMn orbitals, correlates well with the largest elements in the differential low-spin vs high-spin entanglement map. These elements correspond to interactions between the pairs of dMn orbitals mediated by the oxo-bridging out-of-plane p orbitals, representing the πsuperexchange pathway. We also show that the reduction of active space to manifold of the singly occupied magnetic orbitals does not lead to discrepancy between the calculated J values and entanglement maps. This contrasts to analysis of mutual information, which suggests the 'direct'dMn-dMn interactions to play a dominant role for the J coupling, irrespective of the size of active space as well as of the antiferromagnetism expected. The failure is attributed to the large contribution of spin entanglement contained in the mutual information of the low-spin state, which may be regarded as the origin of the different complexity of its wave function and electron density. Workplace Institute of Organic Chemistry and Biochemistry Contact asep@uochb.cas.cz ; Kateřina Šperková, Tel.: 232 002 584 ; Jana Procházková, Tel.: 220 183 418 Year of Publishing 2022 Electronic address https://doi.org/10.1021/acs.jpclett.0c03652
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