Selecting Quantum-Chemical Methods for Lanthanide-Containing Molecules: A Balance between Accuracy and Efficiency

Abstract

An analysis of how different density functionals, basis sets, and relativistic approximations affect the computed properties of lanthanide-containing molecules allows one to determine which method provides the highest accuracy. Historically, many different density functional methods have been employed to perform calculations on lanthanide complexes and so herein is a detailed analysis of how different methodological combinations change the computed properties of three different families of lanthanide-bearing species: lanthanide diatomic molecules (fluorides and oxides) and their dissociation energies; larger, molecular complexes and their geometries; and lanthanide bis(2-ethylhexyl)phosphate structures and their separation free energies among the lanthanide series. The B3LYP/Sapporo/Douglas−Kroll−Hess (DKH) method was shown to most accurately reproduce dissociation energies calculated at the CCSDT(Q) level of theory with a mean absolute deviation of 1.3 kcal/mol. For the calculations of larger, molecular complexes, the TPSSh/Sapporo/DKH method led to the smallest deviation from experimentally refined crystal structures. Finally, this same method led to calculated separation factors for lanthanide bis(2ethylhexyl)phosphate structures that matched very closely with experimental values.

The solution structures and relative stability constants of lanthanide–EDTA complexes predicted from computation

“…Ln-ligand complex stability can be determined experimentally with stability constant measurements, 3 or computationally with binding energy calculations. [4][5][6][7] Relative binding energies can be compared to relative stability constants and be used to predict ligand selectivity to a particular Ln 3+ ion.…”

Computational workflows for novel materials: Case study for lanthanide manganese perovskites

“…[52] Instead, we first focus on calculating the equilibrium bond lengths (r e ) in diatomic lanthanide oxides and halides, in analogy with Ref. 53.…”

Quantum Computing and Simulations for Energy Applications: Review and Perspective

“…Candidate sensing materials such as MOFs , and biomolecules are computationally expensive to screen due to their complexity and size. Quantum computers may therefore supplement ongoing efforts to computationally design and screen potential metal extraction agents. , Studies currently underway apply quantum computers for material design , and modeling binding site interactions, and similar techniques may be applied to develop highly selective chelation agents.…”