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Improving the calculation of magnetic coupling constants in MRPT methods
Author(s) -
Spivak Mariano,
Angeli Celestino,
Calzado Carmen J.,
Graaf Coen
Publication year - 2014
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23672
Subject(s) - atomic orbital , delocalized electron , slater type orbital , perturbation theory (quantum mechanics) , coupling constant , coupling (piping) , unpaired electron , natural bond orbital , inductive coupling , molecular orbital , physics , atomic physics , computational chemistry , chemistry , quantum mechanics , electron , molecular orbital theory , density functional theory , materials science , molecule , metallurgy
The magnetic coupling in transition metal compounds with more than one unpaired electron per magnetic center has been studied with multiconfigurational perturbation theory. The usual shortcomings of these methodologies (severe underestimation of the magnetic coupling) have been overcome by describing the Slater determinants with a set of molecular orbitals that maximally resemble the natural orbitals of a high‐level multiconfigurational reference configuration interaction calculation. These orbitals have significant delocalization tails onto the bridging ligands and largely increase the coupling strengths in the perturbative calculation. © 2014 Wiley Periodicals, Inc.