Overlap integrals and excitation energies calculations in trivalent lanthanides 4f orbitals in pairs Ln-L (L = Ln, N, O, F, P, S, Cl, Se, Br, and I)

Abstract

In this work, DFT-based calculations of overlap integrals (ρ) and excitations energies (Δε) associated with the diatomic-like pairs Ln3+-Ligand and Ln-Ln’ are presented. The ρ and Δε quantities are useful for the calculations of overlap polarizability, charge factors, intensity parameters (using the Simple Overlap and Bond Overlap models), 4f shielding factors, and energy transfer process (ligand-to-Ln and Ln-Ln). A comprehensive set of parametric curves of the type exp(a + bR + cR2) are presented to easily determine these properties at a given distance R. Some literature is presented to indicate the importance of ρ and Δε quantities in photophysical properties of lanthanide-based compounds.