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Title: Post-B3LYP Functionals Do Not Improve the Description of Magnetic Coupling in Cu(II) Dinuclear Complexes
Author: Costa Sala, Ramon
Reta Mañeru, Daniel
Moreira, Ibério de Pinho Ribeiro
Illas i Riera, Francesc
Keywords: Compostos complexos
Química nuclear
Complex compounds
Nuclear chemistry
Issue Date: 5-Apr-2018
Publisher: American Chemical Society
Abstract: The accuracy of post-B3LYP functionals is analyzed using an open-shell database of Cu(II) dinuclear complexes with well-defined experimental values of the magnetic coupling constants. This database provides a sound open-shell training set to be used to improve the fitting schemes in defining new functionals or when reparametrizing the existing ones. For a large set of representative hybrid exchange-correlation functionals, it is shown that the overall description of moderate-to-strong antiferromagnetic interactions is significantly more accurate than the description of ferromagnetic or weakly antiferromagnetic interactions. In the case of global hybrids, the most reliable ones have 25-40% Fock exchange with SOGGA and PBEO being the most reliable and M06 the exception. For range-corrected hybrids, the long-range corrected CAM-B3LYP and omega B97XD provide acceptable results, and M11 is comparable but more erratic. It is concluded that the reliability of the calculated values is system and range-dependent, and this fact introduces a serious warning on the blind use of a single functional to predict magnetic coupling constants. Hence, to extract acceptable magnetostructural correlations, a 'standardization' of the method to be used is advised to choose the optimal functional.
Note: Versió postprint del document publicat a:
It is part of: Journal of Physical Chemistry A, 2018, vol. 122, num. 13, p. 3423-3432
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ISSN: 1089-5639
Appears in Collections:Articles publicats en revistes (Institut de Química Teòrica i Computacional (IQTCUB))
Articles publicats en revistes (Química Inorgànica i Orgànica)
Articles publicats en revistes (Ciència dels Materials i Química Física)

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