A litmus test for the balanced description of dispersion interactions and coordination chemistry of lanthanoids

Abstract

The influence of long-range interactions on the structure of complexes of Eu(iii) with four 9-hydroxy-phenalen-1-one ligands (HPLN) and one alkaline earth metal dication [Eu(PLN)4AE]+ (AE: Mg, Ca, Sr, and Ba) is analyzed.

Cryogenic Ion Vibrational Predissociation (CIVP) Spectroscopy of Aryl Cobinamides in the Gas Phase: How Good Are the Calculations for Vitamin B12 Derivatives?

“…A crude, if still effective, test comes from the search for the minimum energy structures for αEtPhCbi + and βEtPhCbi + with BP86/def2-TZVP, in which the removal of the D3 correction reduces the long-range attractive part of the van der Waals potential. Many benchmark studies find that the typical DFT functionals, BP86 among them, systematically underestimate attractive forces in the 3–5 Å range. ,,− Recent work on a variety of test systems using multiple different experimental techniques suggests strongly that the D3 correction overestimates that attractive interaction, at the very least for certain interaction geometries . However, one may judge the evidence, it is probably fair to claim that the physically most realistic treatment for London dispersion interactions lies somewhere between no D3 and 100% D3, most likely toward the higher end but not necessarily uniformly for all interactions at all geometries.…”

“… 25 , 26 , 69 − 71 Recent work on a variety of test systems using multiple different experimental techniques suggests strongly that the D3 correction overestimates that attractive interaction, at the very least for certain interaction geometries. 72 However, one may judge the evidence, it is probably fair to claim that the physically most realistic treatment for London dispersion interactions lies somewhere between no D3 and 100% D3, most likely toward the higher end but not necessarily uniformly for all interactions at all geometries. Taking this situation as a starting point, one may test for robustness in the optimized structure, i.e.…”