Zero-field splitting in nickel(II) complexes : A comparison of DFT and multi-configurational wavefunction calculations

The zero-field splitting (ZFS) is an important quantity in the electron spin Hamiltonian for S = 1 or higher. We report calculations of the ZFS in some six- and five-coordinated nickel(II) complexes (S = 1), using different levels of theory within the framework of the ORCA program package [F. Neese,...

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Bibliographic Details
Published in:The Journal of Chemical Physics
Main Authors: Kubica, A., Kowalewski, Jozef, Kruk, D., Odelius, Michel
Format: Article in Journal/Newspaper
Language:English
Published: Stockholms universitet, Institutionen för material- och miljökemi (MMK) 2013
Subjects:
Physical Sciences
Fysik
Chemical Sciences
Kemi
Orca
Online Access:http://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-87610
https://doi.org/10.1063/1.4790167
Description
Summary:The zero-field splitting (ZFS) is an important quantity in the electron spin Hamiltonian for S = 1 or higher. We report calculations of the ZFS in some six- and five-coordinated nickel(II) complexes (S = 1), using different levels of theory within the framework of the ORCA program package [F. Neese, Wiley Interdiscip. Rev.: Comput. Mol. Sci. 2, 73 (2012)]10.1002/wcms.81. We compare the high-end ab initio calculations (complete active space self-consistent field and n-electron valence state perturbation theory), making use of both the second-order perturbation theory and the quasi-degenerate perturbation approach, with density functional theory (DFT) methods using different functionals. The pattern of results obtained at the ab initio levels is quite consistent and in reasonable agreement with experimental data. The DFT methods used to calculate the ZFS give very strongly functional-dependent results and do not seem to function well for our systems.

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