Magnetic Resonance Parameters of Radicals Studied by Density Functional Theory Methods

Sammanfattning: The recent state of art in the magnetic resonance area putsforward the electron paramagnetic resonance, EPR, and nuclearmagnetic resonance, NMR, experiments on prominent positions forinvestigations of molecular and electronic structure. A mostdifficult aspect of such experiments is usually the properinterpretation of data obtained from high-resolution spectra,that, however, at the same time opens a great challenge forpure theoretical methods to interpret the spectral features.This thesis constitutes an effort in this respect, as itpresents and discusses calculations of EPR and NMR parametersof paramagnetic molecules. The calculations are based on newmethodology for determination of properties of paramagneticmolecules in the framework of the density functional theory,which has been developed in our laboratory.Paramagnetic molecules are, in some sense, very special. Thepresence of unpaired electrons essentially modifies theirspectra. The experimental determination of the magneticresonance parameters of such molecules is, especially in theNMR case, quite complicated and requires special techniques ofspectral detection. The significant efforts put into suchexperiments are completely justi fied though by the importantroles of paramagnetic species playing in many areas, such as,for example, molecular magnets, active centers in biologicalsystems, and defects in inorganic conductive materials.The first two papers of this thesis deal with thetheoretical determination of NMR parameters, such as thenuclear shielding tensors and the chemical shifts, inparamagnetic nitroxides that form core units in molecularmagnets. The developed methodology aimed to realize highaccuracy in the calculations in order to achieve successfulapplications for the mentioned systems. Theeffects of hydrogenbonding are also described in that context. Our theory forevaluation of nuclear shielding tensors in paramagneticmolecules is consistent up to the second order in the finestructure constant and considers orbital, fully isotropicdipolar, and isotropic contact contributions to the shieldingtensor.The next three projects concern electron paramagneticresonance. The wellknown EPR parameters, such as the g-tensorsand the hyperfine coupling constants are explored. Calculationsof electronic g-tensors were carried out in the framework of aspin-restricted open-shell Kohn-Sham method combined with thelinear response theory recently developed in our laboratory.The spincontamination problem is then automatically avoided.The solvent effects, described by the polarizable continuummodel, are also considered. For calculations of the hyperfinecoupling constants a so-called restricted-unrestricted approachhas been developed in the context of density functional theory.Comparison of experimentally and theoretically determinedparameters shows that qualitative mutual agreement of the twosets of data can be easily achieved by employing the proposedformalisms.