Small Amount Makes a Big Difference: Critical (n - 1)d Valence Orbitals of Heavy Alkaline Earth Metals inside Cage Clusters.
Le YangXiaojiao GuBo LiKai NiuPeng JinPublished in: Inorganic chemistry (2021)
Heavy alkaline earth metals (Aes) are usually considered to engage in chemical bonding by donating the two electrons on ns atomic orbitals (AOs). In this work, a series of typical endohedrally doped cage clusters Ae@cage (Ae = Ca, Sr, Ba; cage = C32, C74, C94, B40, Si20, Sn12, Au16) were thoroughly investigated by means of density functional theory calculations. We found that their occupied molecular orbitals have ∼1 to 14% contributions from Ae-(n - 1)d AOs due to electron back-donation from the cage. Though the amount is small, it is hard to ignore: with the d orbitals, all these endohedral clusters exhibit obviously shortened Ae-cage distances, greatly enhanced encapsulation stabilities, changed highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps, and much lowered Ae valences far from ideal +2. Evidently, the valence orbitals of Ca/Sr/Ba in these systems should include both ns and (n - 1)d. By disclosing the critical role of unnoticed metal orbitals, our work provides completely new insights into the cluster field.