Your browser doesn't support javascript.
loading
Intermolecular Covalent Interactions: Nature and Directionality.
de Azevedo Santos, Lucas; Ramalho, Teodorico C; Hamlin, Trevor A; Bickelhaupt, F Matthias.
Affiliation
  • de Azevedo Santos L; Department of Theoretical Chemistry, Amsterdam Institute for Molecular and Life Sciences (AIMMS), Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.
  • Ramalho TC; Department of Chemistry, Institute of Natural Sciences, Federal University of Lavras CEP, 37200-900, Lavras, MG, Brazil.
  • Hamlin TA; Center for Basic and Applied Research, University Hradec Kralove, Hradec Kralove, Czech Republic.
  • Bickelhaupt FM; Department of Theoretical Chemistry, Amsterdam Institute for Molecular and Life Sciences (AIMMS), Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.
Chemistry ; 29(14): e202203791, 2023 Mar 07.
Article in En | MEDLINE | ID: mdl-36478415
Quantum 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 Fm Z⋅⋅⋅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 H2 ClSb⋅⋅⋅NH3 complexes.
Key words

Full text: 1 Collection: 01-internacional Database: MEDLINE Language: En Journal: Chemistry Journal subject: QUIMICA Year: 2023 Document type: Article Affiliation country: Netherlands Country of publication: Germany

Full text: 1 Collection: 01-internacional Database: MEDLINE Language: En Journal: Chemistry Journal subject: QUIMICA Year: 2023 Document type: Article Affiliation country: Netherlands Country of publication: Germany