Do nonmetallic superalkali cations exist?

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Superalkalis are clusters or molecules featuring lower ionization energies (IEs) than that of cesium atoms, and thus exhibit excellent reducing properties. Such special species have great potential to be used in the synthesis of unusual charge‐transfer salts and cluster‐assembled nanomaterials with tailored properties, in the reduction of carbon dioxide, or as hydrogen storage materials and noble‐gas‐trapping agents, etc. In this regard, ongoing efforts have been devoted to designing and characterizing superalkalis of new types. The recent progress on the study of superalkalis in terms of theoretical design, characterization, and potential application is summarized in this minireview. We hope this review will not only provide a broad overview of this research field, but also highlight the prospect of further extending the experimental synthesis and practical application of superalkalis.

Section: Theoretical Design Of Superalkalismentioning

confidence: 99%

Section: Theoretical Design Of Superalkalismentioning

confidence: 99%

Section: Characterization Of Superalkalismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Recent Progress on the Design, Characterization, and Application of Superalkalis

Sun

2019

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On the Possibility of Using the Jellium Model as a Guide To Design Bimetallic Superalkali Cations

Sun

Pan

Chen

et al. 2019

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The potential application of the jellium model as guidance in the rational design of bimetallic superalkali cations is examined under gradient‐corrected density functional theory for the first time. By using Li, Mg, and Al as atomic building blocks, a series of bimetallic cationic clusters with 2, 8, 20, and 40 valence electrons are obtained and investigated. As the corresponding neutral clusters tend to lose one valence electron to achieve closed‐shell states in the jellium model, these studied cations exhibit much lower vertical electron affinities (EAvert, 3.42–4.95 eV) than the ionization energies (IEs) of alkali metal atoms, indicating their superalkali identities. The high stability of these cationic clusters is guaranteed by their considerable HOMO–LUMO gaps and binding energies per atom. Moreover, the feasibility of using the designed superalkalis as efficient reductants to activate CO2 and N2 molecules and as stable building blocks to assemble ionic superatom compounds is explored. Therefore, this study may provide an effective method for obtaining various metallic superatoms with extensive applications on the basis of the simple jellium rule.

Superalkalis with Hydrogen as Central Electronegative Atom and their Possible Applications: Ab Initio and DFT Study

Sarkar,

Debnath,

Das

2024

Superalkalis are unusual species having ionization energies lower than that of the alkali metals. These species with various applications are of great importance in chemistry due to their low ionization energies and strong reducing property. A typical superalkali contains a central electronegative core decorated with excess metal ligands. In the quest for novel superalkalis, we have designed the superalkalis HLi2, HLiNa and HNa2 using hydrogen as central electronegative atom for the first time employing high level ab initio (CCSD(T), MP2) and density functional theory (ωB97X‐D) methods. The superalkalis exhibit very low ionization energies, even lower than that of cesium. Stability of these species is verified from binding energy and dissociation energy values. The superalkalis are capable of reducing SO2, NO, CO2, CO and N2 molecules by forming stable ionic complexes and therefore can be used as catalysts for the reduction or activation of systems possessing very low electron affinities. The superalkalis form stable supersalts with tailored properties when interact with a superhalogen. They also show remarkably high non‐linear optical responses, hence could have industrial applications. It is hoped that this work will enrich the superalkali family and spur further theoretical and experimental research in this direction.