Intermolecular covalent interactions: nature and directionality

Registro completo de metadados
MetadadosDescriçãoIdioma
Autor(es): dc.creatorSantos, Lucas de Azevedo-
Autor(es): dc.creatorRamalho, Teodorico C.-
Autor(es): dc.creatorHamlin, Trevor A.-
Autor(es): dc.creatorBickelhaupt, F. Matthias-
Data de aceite: dc.date.accessioned2026-02-09T11:42:36Z-
Data de disponibilização: dc.date.available2026-02-09T11:42:36Z-
Data de envio: dc.date.issued2023-07-11-
Data de envio: dc.date.issued2023-07-11-
Data de envio: dc.date.issued2022-
Fonte completa do material: dc.identifierhttps://repositorio.ufla.br/handle/1/58107-
Fonte completa do material: dc.identifierhttps://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.202203791-
Fonte: dc.identifier.urihttp://educapes.capes.gov.br/handle/capes/1145726-
Descrição: dc.descriptionQuantum chemical methods were employed to analyze the nature and the origin of the directionality of pnictogen (PnB), chalcogen (ChB), and halogen bonds (XB) in archetypal FmZ⋅⋅⋅F− complexes (Z=Pn, Ch, X), using relativistic density functional theory (DFT) at ZORA-M06/QZ4P. Quantitative Kohn-Sham MO and energy decomposition analyses (EDA) show that all these intermolecular interactions have in common that covalence, that is, HOMO−LUMO interactions, provide a crucial contribution to the bond energy, besides electrostatic attraction. Strikingly, all these bonds are directional (i.e., F−Z⋅⋅⋅F− is approximately linear) despite, and not because of, the electrostatic interactions which, in fact, favor bending. This constitutes a breakdown of the σ-hole model. It was shown how the σ-hole model fails by neglecting both, the essential physics behind the electrostatic interaction and that behind the directionality of electron-rich intermolecular interactions. Our findings are general and extend to the neutral, weaker ClI⋅⋅⋅NH3, HClTe⋅⋅⋅NH3, and H2ClSb⋅⋅⋅NH3 complexes.-
Idioma: dc.languageen-
Publicador: dc.publisherhttps://chemistry-europe.onlinelibrary.wiley.com/doi/full/10.1002/chem.202203791-
Direitos: dc.rightsrestrictAccess-
???dc.source???: dc.sourceChemistry-A European Journal-
Palavras-chave: dc.subjectBond theory-
Palavras-chave: dc.subjectChalcogen bonds-
Palavras-chave: dc.subjectDensity functional calculations-
Palavras-chave: dc.subjectHalogen bonds-
Palavras-chave: dc.subjectPnictogen bonds-
Título: dc.titleIntermolecular covalent interactions: nature and directionality-
Tipo de arquivo: dc.typeArtigo-
Aparece nas coleções:Repositório Institucional da Universidade Federal de Lavras (RIUFLA)

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