Multicenter (FX)n/NH3 halogen bonds (X = Cl, Br and n = 1–5). QTAIM descriptors of the strength of the X…N interaction

In the present work an in depth deep electronic study of multicenter XBs (FX)n/NH3 (X = Cl, Br and n = 1–5) is conducted. The ways in which X X lateral contacts affect the electrostatic or covalent nature of the X N interactions are explored at the CCSD(T)/aug-cc-pVTZ level and in the framewo...

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Autores principales: Buralli, Gabriel Jesús, Petelski, André N., Peruchena, Nélida María, Sosa, Gladis Laura, Duarte, Darío Jorge Roberto
Formato: Artículo
Lenguaje:Inglés
Publicado: Molecular Diversity Preservation International 2021
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Acceso en línea:http://repositorio.unne.edu.ar/handle/123456789/27925
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Sumario:In the present work an in depth deep electronic study of multicenter XBs (FX)n/NH3 (X = Cl, Br and n = 1–5) is conducted. The ways in which X X lateral contacts affect the electrostatic or covalent nature of the X N interactions are explored at the CCSD(T)/aug-cc-pVTZ level and in the framework of the quantum theory of atoms in molecules (QTAIM). Calculations show that relatively strong XBs have been found with interaction energies lying between 41 and 90 kJ mol 1 for chlorine complexes, and between 56 and 113 kJ mol 1 for bromine complexes. QTAIM parameters reveal that in these complexes: (i) local (kinetics and potential) energy densities measure the ability that the system has to concentrate electron charge density at the intermolecular X N region; (ii) the delocalization indices [ (A,B)] and the exchange contribution [VEX(X,N)] of the interacting quantum atoms (IQA) scheme, could constitute a quantitative measure of the covalence of these molecular interactions; (iii) both classical electrostatic and quantum exchange show high values, indicating that strong ionic and covalent contributions are not mutually exclusive.