On the sensitivity of f electrons to their chemical environment.

摘要: Density functional calculations have been carried out on three families of lanthanide complexes D3 or C4 symmetry, namely [Ln(H2O)9]3+, [Ln(DPA)3]3-, and [Ln(DOTAM)]3+ (Ln = Y, La, Lu; DPA pyridine-2,6-dicarboxylate; DOTAM 1,4,7,10-tetracarbamoylmethyl-1,4,7,10-tetraazacyclododecane), to get some insights concerning the sensitivity 4f electrons surrounding ligands. We show that electron density accumulations found within 0.7 A metal center, precisely give opposite image coordination sphere as they are located trans with respect Ln-ligand bonds, almost exclusively due f electrons. This polarization in lanthanides has therefore be considered a general feature plays crucial role experimentally observed phenomenons such dependency quadratic hyperpolarizability number [Ln(DPA)3]3- we evidenced.