{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,9]],"date-time":"2026-10-09T01:11:45Z","timestamp":1791508305418,"version":"4.3.4"},"reference-count":102,"publisher":"American Chemical Society (ACS)","issue":"2","license":[{"start":{"date-parts":[[2019,2,12]],"date-time":"2019-02-12T00:00:00Z","timestamp":1549929600000},"content-version":"vor","delay-in-days":28,"URL":"https:\/\/pubs.acs.org\/page\/policy\/authorchoice_ccby_termsofuse.html"}],"funder":[{"DOI":"10.13039\/501100004189","name":"Max-Planck-Gesellschaft","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/501100004189","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2019,2,12]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Face-sharing octahedral dinuclear Cr(III) compounds with d3\u2013d3 electronic configurations represent nontrivial examples of electronic complexity, posing particular challenges for theoretical and computational studies. A tris-hydroxy-bridged Cr(III)\u2013Cr(III) system has proven to be a richly rewarding target for studies of magnetism and electron paramagnetic resonance spectroscopy. It was also reported to be a peculiarly difficult system to treat with density functional theory (DFT). In this work the magnetic coupling problem for this dimer is approached with broken-symmetry (BS)-DFT and multireference calculations that utilize the density matrix renormalization group (DMRG) to handle full-valence active spaces. BS-DFT is shown to recover the correct ordering and energy spacing of Heisenberg spin states if used in conjunction with appropriate spin projection procedures, albeit with pronounced functional sensitivity. The contrasting conclusions of previous studies are traced to incorrect inclusion of electronically excited configurations. Analysis of the direct and differential overlap of corresponding orbital pairs from the BS-DFT solution indicates that metal\u2013metal through-space interaction is the dominant contributor to antiferromagnetic coupling. At the DFT level a procedure that utilizes pseudopotential substitution is demonstrated that allows evaluation of the direct exchange vs superexchange contributions. A complementary description is obtained with DMRG-SCF calculations that enable state-averaged CASSCF calculations with both metal and bridge orbitals in the active space. A localized orbital subspace analysis supports the DFT conclusions that in contrast to doubly bridged isoelectronic analogues, antiferromagnetic coupling in the chromium dimer arises primarily from direct metal\u2013metal interaction but is significantly enhanced by ligand-mediated superexchange.<\/jats:p>","DOI":"10.1021\/acs.jctc.8b00969","type":"journal-article","created":{"date-parts":[[2019,1,15]],"date-time":"2019-01-15T16:09:10Z","timestamp":1547568550000},"page":"938-948","source":"Crossref","is-referenced-by-count":60,"title":["Meeting the Challenge of Magnetic Coupling in a Triply-Bridged Chromium\nDimer: Complementary Broken-Symmetry Density Functional Theory and\nMultireference Density Matrix Renormalization Group Perspectives"],"prefix":"10.1021","volume":"15","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-2146-9065","authenticated-orcid":true,"given":"Dimitrios A.","family":"Pantazis","sequence":"first","affiliation":[{"name":"Max-Planck-Institut fu\u0308r Kohlenforschung , Kaiser-Wilhelm-Platz 1 , ,","place":["Mu\u0308lheim an der Ruhr, Germany, 45470"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2019,1,15]]},"reference":[{"key":"2026090316583344100_cit1","first-page":"396","volume-title":"Molecular Magnetism","author":"Kahn","year":"1993"},{"key":"2026090316583344100_cit2","doi-asserted-by":"publisher","first-page":"246","DOI":"10.1007\/978-3-319-22951-5","volume-title":"Magnetic Interactions in Molecules\nand Solids","author":"de Graaf","year":"2016"},{"key":"2026090316583344100_cit3","doi-asserted-by":"publisher","first-page":"429","DOI":"10.1021\/cr300500z","article-title":"Magnetic Interactions\nin Molecules and Highly Correlated Materials: Physical Content, Analytical\nDerivation, and Rigorous Extraction of Magnetic Hamiltonians","volume":"114","author":"Malrieu","year":"2014","journal-title":"Chem. 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Chem."},{"key":"2026090316583344100_cit46","doi-asserted-by":"publisher","first-page":"5726","DOI":"10.1021\/ja312552f","article-title":"On the\nMagnetic and Spectroscopic Properties of High-Valent Mn3CaO4 Cubanes as Structural Units of Natural and Artificial\nWater Oxidizing Catalysts","volume":"135","author":"Krewald","year":"2013","journal-title":"J. Am. Chem. Soc."},{"key":"2026090316583344100_cit47","doi-asserted-by":"publisher","first-page":"5108","DOI":"10.1002\/chem.200802456","article-title":"A New Quantum Chemical Approach to the Magnetic Properties of Oligonuclear\nTransition-Metal Complexes: Application to a Model for the Tetranuclear\nManganese Cluster of Photosystem II","volume":"15","author":"Pantazis","year":"2009","journal-title":"Chem. -\nEur. 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