DFT description of the electronic structure and spectromagnetic properties of strongly correlated electronic systems: NiII, CuII and ZnII o-dioxolene complexes |
| |
Authors: | Bencini Alessandro Carbonera Chiara Totti Federico |
| |
Affiliation: | Dipartimento di Chimica, via della Lastruccia 3, Università di Firenze, Sesto Fiorentino, FI, Italy. alessandro.bencini@unifi.it |
| |
Abstract: | The spectroscopic and magnetic properties of dioxolene complexes of zinc, copper and nickel were studied by DFT calculations on model complexes of formulas [(NH(3))(4)M(II)(SQ)](+) (M=Zn, Ni; SQ=semiquinonato) and [(NH(3))(2)Cu(II)(SQ)](+). Standard approaches such as time-dependent DFT (TDDFT), the Slater transition state (STS), and broken symmetry (BS) were found to be unable to completely account for the physical properties of the systems, and complete active space-configuration interaction (CAS-CI) calculations based on the Kohn-Sham (KS) orbitals was applied. The CAS-CI energies, properly corrected with multireference perturbation theory (MR-PT), were found to be in good agreement with experimental data. We present here a calculation protocol that has a low CPU cost/accuracy ratio and seems to be very promising for interpreting the properties of strongly correlated electronic systems in complexes of real chemical size. |
| |
Keywords: | ab initio calculations charge transfer density functional calculations magnetic properties semiquinone complexes |
本文献已被 PubMed 等数据库收录! |
|