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A Glimpse into the Ligand Field Theory from Density Functional Perspective
dc.creator | Zlatar, Matija | |
dc.creator | Gruden, Maja | |
dc.date.accessioned | 2023-03-07T14:07:46Z | |
dc.date.available | 2023-03-07T14:07:46Z | |
dc.date.issued | 2017 | |
dc.identifier.uri | https://cer.ihtm.bg.ac.rs/handle/123456789/5927 | |
dc.description.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. | sr |
dc.language.iso | en | sr |
dc.publisher | Univ. Nova de Lisboa | sr |
dc.publisher | COST Action CM1305 | sr |
dc.relation | COST Action CM1305 - ECOSTBio (Explicit Control Over Spin-states in Technology and Biochemistry) | sr |
dc.rights | openAccess | sr |
dc.rights.uri | https://creativecommons.org/licenses/by/4.0/ | |
dc.source | Book of abstracts - ECOSTBio: Sixth scientific workshop, March 30-31, 2017, Lisboa, Portugal | sr |
dc.subject | electronic structure | sr |
dc.subject | transition metal complexes | sr |
dc.subject | Ligand Field Theory | sr |
dc.subject | LF-DFT | sr |
dc.subject | DFT | sr |
dc.subject | magnetic properties | sr |
dc.subject | Zero-Field Splitting | sr |
dc.title | A Glimpse into the Ligand Field Theory from Density Functional Perspective | sr |
dc.type | conferenceObject | sr |
dc.rights.license | BY | sr |
dc.citation.spage | ST16 | |
dc.citation.rank | M34 | |
dc.identifier.rcub | https://hdl.handle.net/21.15107/rcub_cer_5927 | |
dc.identifier.fulltext | http://cer.ihtm.bg.ac.rs/bitstream/id/24568/A-M34-6.pdf | |
dc.type.version | publishedVersion | sr |