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Simple nonempirical calculations of the zero‐field splitting in transition metal systems: I. The Ni(II)–Water complexes
Author(s) -
Ribbing Carl,
Odelius Michael,
Laaksonen Aatto,
Kowalewski Jozef,
Roos Björn
Publication year - 1990
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560382430
Subject(s) - chemistry , hamiltonian (control theory) , transition metal , open shell , zero field splitting , excitation , ground state , molecule , octahedron , atomic physics , ligand field theory , perturbation theory (quantum mechanics) , electron , computational chemistry , physics , quantum mechanics , ion , spin polarization , mathematical optimization , biochemistry , mathematics , catalysis , organic chemistry
A simple nonempirical scheme is presented for calculating the splittings of ground state multiplets (the zero‐field splitting) in transition metal complexes. The method employs single reference, single excitation CI calculations based on open‐shell RHF . The spin–orbit coupling is described using an effective one‐electron, one‐center operators. The method is applied to the triplet state Ni(II) complexes with one to six water molecules. The validity of the second‐order perturbation theory approach and of the spin‐Hamiltonian formalism is found to be limited to slightly distorted octahedral systems. Generally, small changes in the geometries of the complexes are found to cause substantial variations of the splitting pattern.