Halogen Bonds Stabilised by an Electronic Exchange Channel

The σ-hole is an important concept which has been widely used lately to describe the halogen bond (XB) essentially as electrostatic in nature. However, this idea is not free of controversy. For the sake of this work, localised molecular orbital energy decomposition analysis (LMOEDA), interacting quantum atom (IQA) method and analysis of the electrostatic potential have been applied to O−Cl⋅⋅⋅B (B=CO, PH3, SH2, CS, NH3, OH−) complexes. The results show that in their equilibrium geometry the stabilizing effect that arises from the Pauli exclusion principle is larger in magnitude than the electrostatic interactions. Besides, it appears that an electronic exchange channel is established at a certain approach distance between the monomers.Fil: Miranda, Matias Orlando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; ArgentinaFil: Duarte, Darío Jorge Roberto. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Nordeste. Instituto de Química Básica y Aplicada del Nordeste Argentino. Universidad Nacional del Nordeste. Facultad de Ciencias Exactas Naturales y Agrimensura. Instituto de Química Básica y Aplicada del Nordeste Argentino; Argentin