Authors
Jacob J Wardzala, Younghwan Kim, Rishu Khurana, Mukunda Mandal, Massimiliano Delferro, Cong Liu, Laura Gagliardi
Published in
Journal of the American Chemical Society. Jun 25, 2026. Epub Jun 25, 2026.
Abstract
Methane C-H activation at transition-metal sites often involves electronic structures that challenge conventional single-reference electronic structure descriptions. Although Kohn-Sham density functional theory (DFT) is widely used to study catalytic trends, its reliability for reactions involving strongly correlated species remains uncertain. Here we present a systematic multireference investigation of methane activation at metal-organic framework (MOF) node catalysts across the 3d transition-metal series. We introduce an automated workflow for active space selection to enable consistent application of multireference methods, including multiconfiguration pair-density functional theory and n-electron valence state perturbation theory, to these catalytic systems. These calculations show substantial static correlation in the C-H activation reaction step and predict activation barriers that differ from DFT by 30-70 kJ mol-1, with DFT often qualitatively disagreeing in barrier height trends across transition metals. Analysis of multireference wave functions shows that reactivity is governed by the electronic structure of the M-O moiety along a continuum from metal-oxo to oxyl radical and O biradical character. Increased oxygen-centered spin density and weakened M-O bonding are identified as descriptors of catalytic activity which correlate with lower activation barriers.
PMID:
42345126
Bibliographic data and abstract were imported from PubMed on 25 Jun 2026.
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