Revealing the effect of the oriented external electronic field on the superatom-polymeric Zr3O3 cluster: Superhalogen modulation and spectroscopic characteristics

Seeking novel strategies for designing superatoms is of significance for the potential applications in cluster-assembled nanomaterials. Herein, by employing the density functional theory (DFT) calculations, the effect of the oriented external electronic field (OEEF) on the electronic and photoelectron spectroscopic properties of the superatom-polymeric Zr3O3 cluster was explored. We present the evidence that the increment of the OEEF along all directions results in the remarkable enhancement of the electron affinity (EA) of Zr3O3, which turns it into superhalogen with an EA value of 4.02 eV under 0.020 au OEEF along +y direction. Strikingly, this EA value is larger than that of any halogen atoms in the periodic table. The downward shift of the electronic spectrum induced by the OEEF was confirmed to be the origin of the observed EA enhancement. Furthermore, the investigation of the OEEF's effect on the molecular orbitals (MOs) and photoelectron spectra (PES) of the cluster reveals that the OEEF could alter the electron distribution as well as promoting the blue shift of the PES without changing the spacings between different energetic levels. The OEEF highlighted here provides a new strategy in designing superatoms together with tuning their electronic and spectroscopic properties conveniently and precisely. We wish this finding could stimulate more efforts in designing novel superatoms or superatom-assembled materials from both theory and experiments.