@conference{
author = "Zlatar, Matija and Gruden, Maja",
year = "2017",
abstract = "Electronic structure of transition metal complexes are commonly rationalized within the Ligand Field Theory (LFT). In LFT the Hamiltonian is parameterized in terms of one-electron (LF) parameters and two-electron repulsion integrals (Racaha's parameters) within the manifold of d-electrons. These parameters are determined from a fit to some experimental spectrum. The main drawback of LFT is its empirical nature, thus being limited to a description of the data, and predictions are often restricted to a chemical intuition. To overcome this, hybrid methodology, which combines a multideterminant DFT-based method with LFT, so called LF-DFT, has been developed. At the same time, LF-DFT successfully tackles many shortcomings of standard DFT, including orbital degeneracy and excited states. It works by evaluating DFT energies of all the Slater determinants arising from a dn configuration of the transition-metal ion in the environment of coordinating ligands using Kohn−Sham orbitals. This set of energies is then analyzed within a LF model to obtain variationally the energy and wave function of the ground and excited states. In doing so, both dynamical correlation (via exchange-correlation energy) and non-dynamical correlation (via LF CI) are considered. The quality of the LF-DFT for the calculations of d-d transitions is comparable to the high-level ab initio calculations, and in some cases, e.g. [CrF6]3-, [MnF6]2-, [Mn(H2O)6]2+, [Fe(H2O)6]3+ even outshines them. One of the main strengths of LF-DFT is accurate prediction of magnitude and sign of the Zero-Field Splitting (ZFS) parameters, as well as the orientation of the principal magnetic axes. In addition, we can pin-point the excitations that control the sign and magnitude of the ZFS parameters.Therefore, with a help from DFT based LF theory we can, hopefully, find a way to control the magnetic properties of transition metal complexes.",
publisher = "Univ. Nova de Lisboa, COST Action CM1305",
journal = "Book of abstracts - ECOSTBio: Sixth scientific workshop, March 30-31, 2017, Lisboa, Portugal",
title = "A Glimpse into the Ligand Field Theory from Density Functional Perspective",
pages = "ST16",
url = "https://hdl.handle.net/21.15107/rcub_cer_5927"
}