Electronic and dynamical properties of non-covalent diatomic aggregates formed by He with neutral and ionic Li and Be

Guilherme Carlos Carvalho de Jesus; Caio Vinícius Sousa Costa; Luiz Guilherme Machado de Macedo; Pedro Henrique de Oliveira Neto; Fernando Pirani; Ricardo Gargano

doi:10.1007/s00894-023-05512-9

Electronic and dynamical properties of non-covalent diatomic aggregates formed by He with neutral and ionic Li and Be

J Mol Model. 2023 May 30;29(6):190. doi: 10.1007/s00894-023-05512-9.

Authors

Guilherme Carlos Carvalho de Jesus¹, Caio Vinícius Sousa Costa¹, Luiz Guilherme Machado de Macedo², Pedro Henrique de Oliveira Neto¹, Fernando Pirani^{3

4}, Ricardo Gargano¹

Affiliations

¹ Instituto de Física, Universidade de Brasília (UnB), P.O. Box 04455, Brasília, DF, 70919-970, Brazil.
² Universidade Federal de São João del Rei (UFSJ), Campus Centro Oeste "Dona Lindu" (CCO), Divinópolis, MG, 35501-296, Brazil. lgm@ufsj.edu.br.
³ Dipartimento di Chimica, Biologia e Biotecnologie, Università degli studi di Perugia, via Elce di Sotto 8, Perugia, Italy.
⁴ Dipartimento di Ingegneria Civile ed Ambientale, Università di Perugia, via Duranti 93, 06125, Perugia, Italy.

PMID: 37249738
DOI: 10.1007/s00894-023-05512-9

Abstract

Context and results: This work aims to study the influence of the absence and presence of permanent charges on the electronic and dynamical properties of the non-covalent bound diatomic systems involving He and Li, Be as neutral and ionic partners. The charge displacement results suggest that in the formation of HeLi[Formula: see text], HeBe[Formula: see text], and HeBe[Formula: see text], the neutral He atom undergoes, in the electric field of the ion, a pronounced electronic polarization, and the natural bond order theoretical approach indicates that in the formation of the molecular orbital He acts as a weak electron donor. The energy decomposition analysis provides the dispersion and induction components as the attractive leading terms controlling the stability of all systems, confirming that the formed bond substantially maintains a non-covalent nature which is also supported by the Quantum Theory of Atoms in Molecules (QTAIM) analysis. Finally, it was found that the HeLi and HeBe neutral systems are unstable under any condition, HeLi[Formula: see text] and HeBe[Formula: see text] ionic systems are stable below 317K and 138K, respectively, while the HeBe[Formula: see text] system becomes unstable only after 3045K.

Computational and theoretical techniques: The potential energy curves and interactions in all systems were studied theoretically based on coupled-cluster singles and doubles method with perturbative inclusion of triples CCSD(T) method with an aug-cc-pV5Z basis set. More precisely, it was determined the potential energy curves describing the stability of the HeLi, HeLi[Formula: see text], HeBe, HeBe[Formula: see text], and HeBe[Formula: see text] systems, the charge displacement within the formed adducts, the decomposition of their total interaction energy, the topological analysis of their bonds, their rovibrational energies, their spectroscopic constants and lifetimes.

Keywords: BeLi; Charge displacement; Energy decomposition; HeBe; HeLi; Lifetime; Molecular dynamics; Potential energy curves; Quantum theory of atoms in molecules; and BeLi non-covalent systems.