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The present work employs the complete energy matrices for a d(8) configuration ion in a D(2h) symmetry ligand field at first time to study the relationship between electron paramagnetic resonance (EPR) spectra and local structure of (NiF(6))(4-) coordination complex in Ni(2+):ZnF(2), NiF(2), and Ni(2+):MgF(2) systems, respectively. The crystal field effect on the local structure of the three systems is investigated contrastively by calculating the values of vertical bar partial derivative D'/partial derivative theta vertical bar and vertical bar partial derivative E'/partial derivative theta vertical bar around the (NiF(6))(4-) coordination complex. Moreover, the theoretical values of the g factors of Ni(2+):ZnF(2), NiF(2), and Ni(2+):MgF(2) systems are reported. Simultaneously, the calculated energy levels are in good agreement with the experimental absorption spectra. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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