Summary
A simple non-empirical method is applied to calculate the splittings of the ground state triplet, caused by the spin-orbit coupling, in bis(aquo) bis(malonato) nickel(II), allowing for a certain geometry variation. The calculations yield splittings on the order of 10–20 cm−1. The comparison of exact (within model) and second-order perturbation theory calculations indicate that the spin Hamiltonian formalism is valid. The implications of the results for the theory of nuclear spin relaxation in paramagnetic complexes in solution are discussed.
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Ref. 13 describes calculations for complexes of bis(malonato) Ni(II) with water and ammonia. Going through the geometry parameters used in ref. 13, we found that the calculations for the ammonia complex contained serious input errors. The results for water complex are however correct and the errors for the ammonia complex should not influence the conclusions of ref. 13
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Ribbing, C., Odelius, M., Kowalewski, J. et al. Simple non-empirical calculations of the zero-field splitting in bis(aquo) bis(malonato) nickel(II). Theoret. Chim. Acta 87, 307–312 (1994). https://doi.org/10.1007/BF01113386
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DOI: https://doi.org/10.1007/BF01113386