Publication details

Role of dynamical polarization of ligand-to-metal charge transfer excitations in ab initio determination of effective exchange parameters


GELLE Alain MUNZAROVÁ Markéta LEPETIT Marie-Bernadette ILLAS Francesc

Year of publication 2003
Type Article in Periodical
Magazine / Source Physical Review B
MU Faculty or unit

Faculty of Science

Field Physical chemistry and theoretical chemistry
Keywords Heisenberg coupling; ligand-to-metal charge transfer; DDCI; ab initio; effective exchange
Description The role of the bridging ligand on the effective Heisenberg coupling parameters is analyzed in detail. This analysis strongly suggests that the ligand-to-metal charge transfer excitations are responsible for a large part of the final value of the magnetic coupling constant. This permits us to suggest a variant of the difference dedicated configuration interaction (DDCI) method, presently one of the most accurate and reliable for the evaluation of magnetic effective interactions. This method treats the bridging ligand orbitals mediating the interaction at the same level than the magnetic orbitals and preserves the high quality of the DDCI results while being much less computationally demanding. The numerical accuracy of the new approach is illustrated on various systems with one or two magnetic electrons per magnetic center. The fact that accurate results can be obtained using a rather reduced configuration interaction space opens the possibility to study more complex systems with many magnetic centers and/or many electrons per center.
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