Applications of Density Functional Theory (DFT) to Investigate the Structural, Spectroscopic and Magnetic Properties of Lanthanide(III) Complexes

Abstract

Density functional theory (DFT) has become a general tool to investigate the structure and properties of complicated inorganic molecules, such as lanthanide(III) coordination compounds, due to the high accuracy that can be achieved at relatively low computational cost. Herein, we present an overview of different successful applications of DFT to investigate the structure, dynamics, vibrational spectra, NMR chemical shifts, hyperfine interactions, excited states, and magnetic properties of lanthanide(III) complexes. We devote particular attention to our own work on the conformational analysis of LnIII-polyaminocarboxylate complexes. Besides, a short discussion on the different approaches used to investigate lanthanide(III) complexes, i. e. all-electron relativistic calculations and the use of relativistic effective core potentials (RECPs), is also presented. The issue of whether the 4f electrons of the lanthanides are involved in chemical bonding or not is also shortly discussed.

Characterization and Luminescence Properties of Lanthanide-Based Polynuclear Complexes Nanoaggregates

“…To evaluate this influence of 6 ] 2+ was taken to keep electrostatic interactions of the surrounding lanthanide ions onto the Eu 3+ electronic structure. 80 The study of the electronic structures represented in Figure 3 gives rise to additional excited states in the same energy region than the usual ones issued from pure f−f transitions. The associated oscillator strengths of those excitations are calculated to be larger, rendering them more probable to be populated.…”

A Bis(pyridine N‐oxide) Analogue of DOTA: Relaxometric Properties of the GdIII Complex and Efficient Sensitization of Visible and NIR‐Emitting Lanthanide(III) Cations Including PrIII and HoIII

“…Based on previous experience, the effective core potential (ECP) of Dolg et al. and the related [5s4p3d]‐GTO valence basis set were applied in these calculations 37. This ECP includes 46+4f n electrons in the core, leaving the outermost 11 electrons to be treated explicitly.…”

Understanding Stability Trends along the Lanthanide Series

“…The use of LCRECP has been justified by the fact that 4f orbitals do not significantly contribute to bonding owing to their limited radial extension relative to the 5d and 6s shells. [28,29] LCRECP calculations were shown to provide good results in DFT studies that focus on the structure, dynamics, and estimates of relative energies of Ln 3+ complexes. [30] Since LCRECP calculations include the 4f electrons in the core, they were conducted on a pseudosinglet state configuration.…”