| MUNZAROVÁ, Markéta, Pavel KUBÁČEK and Martin KAUPP. Mechanisms of EPR Hyperfine Coupling in Transition Metal Complexes. The Journal of the American Chemical Society. Washington, D.C.: American Chemical Society, 2000, vol. 122, No 48, p. 11900-11913. ISSN 0002-7863. |
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@article{344294,
author = {Munzarová, Markéta and Kubáček, Pavel and Kaupp, Martin},
article_location = {Washington, D.C.},
article_number = {48},
keywords = {Density functional theory; EPR parameters; hyperfine coupling constants; transition metal complexes; spin polarization},
language = {eng},
issn = {0002-7863},
journal = {The Journal of the American Chemical Society},
title = {Mechanisms of EPR Hyperfine Coupling in Transition Metal Complexes},
volume = {122},
year = {2000}
}
TY - JOUR
ID - 344294
AU - Munzarová, Markéta - Kubáček, Pavel - Kaupp, Martin
PY - 2000
TI - Mechanisms of EPR Hyperfine Coupling in Transition Metal Complexes
JF - The Journal of the American Chemical Society
VL - 122
IS - 48
SP - 11900
EP - 11900
PB - American Chemical Society
SN - 00027863
KW - Density functional theory
KW - EPR parameters
KW - hyperfine coupling constants
KW - transition metal complexes
KW - spin polarization
N2 - 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 UHF wave functions or hybrid density functionals. The role of core- and valence-shell spin polarization for dipolar hyperfine couplings in transition metal complexes is discussed. It is demonstrated that great care should be exercised in deriving spin populations or even orbital compositions from dipolar couplings alone.
ER -
MUNZAROVÁ, Markéta, Pavel KUBÁČEK and Martin KAUPP. Mechanisms of EPR Hyperfine Coupling in Transition Metal Complexes. \textit{The Journal of the American Chemical Society}. Washington, D.C.: American Chemical Society, 2000, vol.~122, No~48, p.~11900-11913. ISSN~0002-7863.
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