{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,15]],"date-time":"2026-06-15T14:10:13Z","timestamp":1781532613698,"version":"3.54.5"},"reference-count":33,"publisher":"Wiley","issue":"16","license":[{"start":{"date-parts":[[2026,6,6]],"date-time":"2026-06-06T00:00:00Z","timestamp":1780704000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"},{"start":{"date-parts":[[2026,6,6]],"date-time":"2026-06-06T00:00:00Z","timestamp":1780704000000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100001321","name":"National Research Foundation","doi-asserted-by":"publisher","award":["CPRR240318209767"],"award-info":[{"award-number":["CPRR240318209767"]}],"id":[{"id":"10.13039\/501100001321","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100004765","name":"Universiteit van die Vrystaat","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100004765","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["J Comput Chem"],"published-print":{"date-parts":[[2026,6,15]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    The Jahn\u2013Teller (JT) effect plays a central role in determining the structure and electronic properties of open\u2010shell transition\u2010metal complexes, yet its reliable theoretical description remains sensitive to the choice of density functional, basis set, and molecular model. In close analogy to the well\u2010established behavior of d\n                    <jats:sup>9<\/jats:sup>\n                    Cu(II) systems, low\u2010spin d\n                    <jats:sup>7<\/jats:sup>\n                    Ni(III) complexes exhibit an E\u2009\u2297\u2009e vibronic instability that gives rise to a multidimensional (\u201cMexican hat\u201d) potential energy surface and dynamic Jahn\u2013Teller behavior. In this work, we present a systematic density functional theory investigation of the Jahn\u2013Teller effect in a series of seven pseudo\u2010octahedral Ni(III) complexes bearing bidentate ligands with O,O or N,N donor atoms, of varying size and rigidity. Geometry optimizations initiated from both axially elongated and compressed starting structures were performed under symmetry constraints to map the Jahn\u2013Teller potential energy surface. At the TPSSh\/def2\u2010TZVP level, optimizations from elongated and compressed starting points identify elongated structures as minima and compressed structures as first\u2010order saddle points. The presence of multiple symmetry\u2010equivalent elongated minima and low barriers between them is consistent with a dynamically averaged Jahn\u2013Teller distortion rather than a purely static one. The resulting axial\u2013equatorial bond length differences (\u0394\n                    <jats:italic>R<\/jats:italic>\n                    \u2009\u2248\u20090.16\u20130.23\u2009\u00c5) and Jahn\u2013Teller stabilization energies (\u0394\n                    <jats:italic>E<\/jats:italic>\n                    <jats:sub>JT<\/jats:sub>\n                    \u2009\u2248\u20090.02\u20130.04\u2009eV) indicate a moderate but systematic preference for axial elongation across the ligand series. Frontier molecular orbital and spin density analyses reveal that the distortion is driven by lifting of the\n                    <jats:italic>e<\/jats:italic>\n                    <jats:sub>g<\/jats:sub>\n                    orbital degeneracy in the low\u2010spin d\n                    <jats:sup>7<\/jats:sup>\n                    configuration, with axial elongation stabilizing the predominantly Ni\u2010centered \u2010based HOMO. Comparative calculations using PW6B95\u2010D3, M06, B3LYP, and OLYP functionals, as well as alternative triple\u2010\u03b6 and double\u2010\u03b6 (def2\u2010SVP) basis sets, confirm that the qualitative Jahn\u2013Teller behavior and ligand\u2010dependent trends are robust, while quantitative differences emphasize the importance of hybrid meta\u2010GGA and dispersion\u2010corrected approaches. Continuum solvation calculations (water, acetonitrile, and dichloromethane) demonstrate that solvent effects do not alter the qualitative Jahn\u2013Teller distortion pattern or energetic ordering. In addition, simplified ligand models are shown to reliably reproduce the essential features of the Jahn\u2013Teller distortion when the immediate coordination environment is preserved, offering a computationally efficient strategy for mechanistic and methodological studies, albeit with limitations for quantitative spectroscopic predictions and for capturing intermolecular effects such as dispersion and crystal packing. Overall, the results establish a consistent electronic\u2010structure description of Jahn\u2013Teller distortions in pseudo\u2010octahedral Ni(III) complexes and highlight both the capabilities and limitations of current DFT approaches for treating vibronically active transition\u2010metal systems.\n                  <\/jats:p>","DOI":"10.1002\/jcc.70399","type":"journal-article","created":{"date-parts":[[2026,6,6]],"date-time":"2026-06-06T08:01:42Z","timestamp":1780732902000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Jahn\u2013Teller Distortions in Pseudo\u2010Octahedral Low\u2010Spin Ni(\n                    <scp>III<\/scp>\n                    ) Complexes With O,O or N,N Bidentate Ligands: A\n                    <scp>DFT<\/scp>\n                    Study"],"prefix":"10.1002","volume":"47","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8120-6830","authenticated-orcid":false,"given":"Jeanet","family":"Conradie","sequence":"first","affiliation":[{"name":"Department of Chemistry University of the Free State  Bloemfontein South Africa"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,6,6]]},"reference":[{"key":"e_1_2_11_2_1","doi-asserted-by":"publisher","DOI":"10.1098\/rspa.1937.0142"},{"key":"e_1_2_11_3_1","doi-asserted-by":"publisher","DOI":"10.1017\/CBO9780511524769"},{"key":"e_1_2_11_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100796a044"},{"key":"e_1_2_11_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.19744080213"},{"key":"e_1_2_11_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic00230a025"},{"key":"e_1_2_11_7_1","doi-asserted-by":"publisher","DOI":"10.1039\/B509274D"},{"key":"e_1_2_11_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic50193a042"},{"key":"e_1_2_11_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cs35253b"},{"key":"e_1_2_11_10_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ica.2023.121422"},{"key":"e_1_2_11_11_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.poly.2024.117075"},{"key":"e_1_2_11_12_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejic.201403144"},{"key":"e_1_2_11_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic00190a009"},{"key":"e_1_2_11_14_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic00102a001"},{"key":"e_1_2_11_15_1","doi-asserted-by":"publisher","DOI":"10.1039\/b008720n"},{"key":"e_1_2_11_16_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2008.05.014"},{"key":"e_1_2_11_17_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.91.146401"},{"key":"e_1_2_11_18_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1626543"},{"key":"e_1_2_11_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp050536c"},{"key":"e_1_2_11_20_1","volume-title":"Gaussian 16, Revision C.01","author":"Frisch M. 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