Novel supersalts formed by interaction of H 2 M 3 superalkalis (M = Li and Na) with AlF 4,BeF 3 and NO 3 superhalogens

Abstract

Supersalts are ionic compounds formed by pairing superalkali cations with superhalogen anions, resulting in systems with strong charge-transfer characteristics. This study investigates novel supersalts of the form H₂M₃–Y (M = Li or Na; Y = AlF₄, BeF₃, NO₃) using the MP2/aug-cc-pVTZ level of theory. Their stability was evaluated via binding energy (E_b) and dissociation energy (E_d), with H₂Li₃–AlF₄ showing the highest binding energy (11.35 eV), followed by H₂Li₃-BeF₃ (10.66 eV) and H₂Li₃-NO₃ (7.58 eV). Net charge analysis confirms significant charge separation (+0.93e / −0.92e in Li systems), supporting the ionic nature of these complexes, further validated by QTAIM analysis. The HOMO–LUMO gap is highest for H₂Li₃–BeF₃ (10.33 eV), indicating relatively higher electronic stability. The results indicate that Li-based supersalts are more stable than their Na-based counterparts, with stability following the trend AlF₄ > BeF₃ > NO₃. These findings provide a basis for understanding charge-transfer-driven molecular systems.

Keywords

superalkalis superhalogen supersalt binding energy QTAIM analysis

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