. "Z(MSM 143100011)" . . "14310" . "US - Spojen\u00E9 st\u00E1ty americk\u00E9" . "716921" . "11900" . "The Journal of the American Chemical Society" . "RIV/00216224:14310/00:00002511" . . . . . "A detailed quantum chemical analysis of the underlying principles of hyperfine coupling in 3d transition metal complexes has been carried out. The explicit evaluation of one- and two-electron integrals for some atomic systems has been used to understand the spin polarization of the core shells. While spin polarization enhances the exchange interaction of the 2s and 2p shells with the singly occupied orbitals, the opposite spin polarization of the 3s and 3p shells arises from the required orthogonality to the 2s and 2p shells, respectively. Core-shell spin polarization in molecules is found to be proportional to the spin population in the valence 3d orbitals but to depend little on other details of bonding. In contrast, the spin polarization of the valence shell depends crucially on the overlap between the singly occupied and certain doubly occupied valence orbitals. Large overlap leads to pronounced spin polarization of these orbitals and, among other things, likely to spin contamination when using UH"@en . . "Mechanisms of EPR Hyperfine Coupling in Transition Metal Complexes" . . "0002-7863" . "[CF85C55D4BF9]" . "48" . "Mechanisms of EPR Hyperfine Coupling in Transition Metal Complexes" . "3"^^ . "0"^^ . "0"^^ . "Mechanisms of EPR Hyperfine Coupling in Transition Metal Complexes"@en . . . "Kaupp, Martin" . . "122" . . "2"^^ . . . "Kub\u00E1\u010Dek, Pavel" . "14"^^ . "Munzarov\u00E1, Mark\u00E9ta" . . . . "Density functional theory, EPR parameters, hyperfine coupling constants, transition metal complexes, spin polarization"@en . "Mechanisms of EPR Hyperfine Coupling in Transition Metal Complexes"@en . . "A detailed quantum chemical analysis of the underlying principles of hyperfine coupling in 3d transition metal complexes has been carried out. The explicit evaluation of one- and two-electron integrals for some atomic systems has been used to understand the spin polarization of the core shells. While spin polarization enhances the exchange interaction of the 2s and 2p shells with the singly occupied orbitals, the opposite spin polarization of the 3s and 3p shells arises from the required orthogonality to the 2s and 2p shells, respectively. Core-shell spin polarization in molecules is found to be proportional to the spin population in the valence 3d orbitals but to depend little on other details of bonding. In contrast, the spin polarization of the valence shell depends crucially on the overlap between the singly occupied and certain doubly occupied valence orbitals. Large overlap leads to pronounced spin polarization of these orbitals and, among other things, likely to spin contamination when using UH" . "RIV/00216224:14310/00:00002511!RIV/2002/MSM/143102/N" .