On the Precise and Continuous Regulation of the Superatomic and Spectroscopic Behaviors of the Quasi-Cubic W₄C₄ Cluster by the Oriented External Electric Field

Abstract

Designing and realizing novel superatoms with controllable and tunable electronic properties is vital for their potential applications in clusterassembly nanomaterials. Here, we investigated the effect of the oriented external electric field (OEEF) on the geometric and electronic structures as well as the spectroscopic properties of the quasi-cubic W 4 C 4 cluster by utilizing the density functional theory (DFT) calculations. Compared with traditional models, the OEEF was observed to hold the special capability in continuously and precisely modulating the electronic properties of W 4 C 4 , that is, remarkably increasing its electron affinity (EA) (1.58 eV) to 5.61 eV under the 0.040 au OEEF (larger than any halogen atoms in the periodic table), which possesses the superhalogen behavior. Furthermore, the downward movement of the lowest unoccupied molecular orbital level of the cluster accompanied by the enhancement of the OEEF intensity was demonstrated to be the origin of the EA increment. Additionally, the photoelectron spectra (PES) of W 4 C 4 − were also simulated under different OEEF intensities, where the PES peaks move to a higher energy area following the enhancement of the OEEF strength, exhibiting the blue-shift behavior. These findings observed here open a new avenue in conveniently and precisely adjusting the electronic properties of clusters, which will be beneficial for the rational design of superatoms or superatom-assembled nanomaterials under the external field.

Unraveling the Solvent Regulation in the Heteroatom-Doped Endohedral Gold Clusters: A Theoretical Study on the Electronic Properties and O2 Activation

“…Among various methods for regulating the electronic properties of clusters, the external field regulation strategy is a novel noninvasive method for modifying the characteristics of clusters. For example, the oriented external electric field has been demonstrated to be able to perform property regulation and design superatoms while preserving their components, geometric structures, valence shell filling, and energetic stability. − In addition, the condensed-phase synthesis of atomically precise clusters has experienced a rapid development in the past decade. − During such a process, the solvent, which has been observed to be able to alter the reactivity of organic reactions to stabilize unstable anions and certain chemical reaction intermediates, is an indispensable external condition during such a synthesis process. Our recent study has shown that polar solvents can act as a novel external field in realizing the superatom design, in which solvents, such as water, with appropriate polarity can convert nonsuperhalogens into superhalogens.…”