{"database":"biostudies-literature","file_versions":[],"scores":null,"additional":{"submitter":["Drosou M"],"funding":["Deutsche Forschungsgemeinschaft","German Academic Exchange Service (DAAD)","French National Research Agency"],"pagination":["e202500317"],"full_dataset_link":["https://www.ebi.ac.uk/biostudies/studies/S-EPMC12640672"],"repository":["biostudies-literature"],"omics_type":["Unknown"],"volume":["26(22)"],"pubmed_abstract":["Paramagnetic molybdenum compounds are of great interest in inorganic chemistry and metalloenzyme catalysis. Electron paramagnetic resonance (EPR) spectroscopies that determine hyperfine coupling constants (HFCs) and g-tensor values are essential for investigating the electronic structure of these compounds, but require support from accurate quantum chemical approaches. Here, a database of Mo(V) complexes with well-defined structures and EPR parameters is presented, and optimal quantum chemical protocols for <sup>95</sup>Mo HFCs and g-values are investigated. It is shown that unmodified segmented all- electron relativistically contracted (SARC) all-electron basis sets can produce converged results for HFCs and g-values with the exact-2-component (X2C) Hamiltonian. The dependence of EPR parameters on the functional is studied in detail. Double-hybrid functionals and global hybrids with high exact exchange are top performers for <sup>95</sup>Mo HFCs, with PBE0-DH achieving the best agreement with experiment. Comparison of density functional theory (DFT)-derived HFCs with values obtained by coupled cluster theory with the domain-based local pair natural orbital approach (DLPNO-CCSD) shows that DFT remains the method of choice for the present set of compounds. Smaller differentiation among functionals is observed for g-tensors, although PBE0-DH is still a top performer and can be recommended as the most reliable approach overall for describing both valence and core properties of Mo compounds."],"journal":["Chemphyschem : a European journal of chemical physics and physical chemistry"],"pubmed_title":["Accurate Calculation of Electron Paramagnetic Resonance Parameters for Molybdenum Compounds."],"pmcid":["PMC12640672"],"funding_grant_id":["57445526","ANR-19-CE05_0030_01","ANR-18 CE092_0040_01","ANR‐18 CE092_0040_01","ANR‐19‐CE05_0030_01"],"pubmed_authors":["Pantazis DA","Orio M","Wehrung I","Drosou M"],"additional_accession":[]},"is_claimable":false,"name":"Accurate Calculation of Electron Paramagnetic Resonance Parameters for Molybdenum Compounds.","description":"Paramagnetic molybdenum compounds are of great interest in inorganic chemistry and metalloenzyme catalysis. Electron paramagnetic resonance (EPR) spectroscopies that determine hyperfine coupling constants (HFCs) and g-tensor values are essential for investigating the electronic structure of these compounds, but require support from accurate quantum chemical approaches. Here, a database of Mo(V) complexes with well-defined structures and EPR parameters is presented, and optimal quantum chemical protocols for <sup>95</sup>Mo HFCs and g-values are investigated. It is shown that unmodified segmented all- electron relativistically contracted (SARC) all-electron basis sets can produce converged results for HFCs and g-values with the exact-2-component (X2C) Hamiltonian. The dependence of EPR parameters on the functional is studied in detail. Double-hybrid functionals and global hybrids with high exact exchange are top performers for <sup>95</sup>Mo HFCs, with PBE0-DH achieving the best agreement with experiment. Comparison of density functional theory (DFT)-derived HFCs with values obtained by coupled cluster theory with the domain-based local pair natural orbital approach (DLPNO-CCSD) shows that DFT remains the method of choice for the present set of compounds. Smaller differentiation among functionals is observed for g-tensors, although PBE0-DH is still a top performer and can be recommended as the most reliable approach overall for describing both valence and core properties of Mo compounds.","dates":{"release":"2025-01-01T00:00:00Z","publication":"2025 Nov","modification":"2026-06-05T18:47:36.639Z","creation":"2026-05-20T03:13:52.803Z"},"accession":"S-EPMC12640672","cross_references":{"pubmed":["41100870"],"doi":["10.1002/cphc.202500317"]}}