A theoretical analysis of linear and bifurcate halogen-oxygen bonds is presented in this work. B3LYP/6-311ϩϩG(d,p) and MP2/6-311ϩϩG(d,p) calculations were used to determine the optimized geometries of intermolecular systems formed by CFCl 3 and O 3 . Molecular properties often analyzed in hydrogen-bonded complexes were used here to describe the interaction between chlorine (CFCl 3 ) and oxygen (O 3 ). The halogen-oxygen bond in the CFCl 3 ⅐⅐⅐O 3 complex was characterized using the topological parameters derived from the quantum theory of atoms in molecules.
B3LYP/6-311++G(d,p) and B3LYP/6-31G(d,p) theoretical levels combined with topological calculations based on the theory of atoms in molecules (AIM) were used to study the formation of intermolecular interactions on heterocyclic hydrogen-bonded complexes formed by ethylene oxide, sulfide oxide, 2,5-dihydrofuran, thiophene, and the hydrofluoric acid. As observed, the electrophilic attack of the hydrofluoric acid occur aligned to the n lone pair of the heteroatom of the cyclic systems, the modeled structure of the hydrogen-bonded complexes is interpreted in terms of the intermolecular parameters of the (n ⋯ HF ) hydrogen bond, such as its R(n ⋯ HF ) distance, ΔE C binding energy, and the new υ(n ⋯ HF ) stretching vibrational mode. From these criteria, a relationship between the strength (R, ΔE C and υ) of the hydrogen bonds and its nonlinearity deviation was verified, which is formed by a secondary interaction between the hydrofluoric acid and axial hydrogen atoms of the cyclic structure. Moreover, even though the Bader's electronic density partitioning has been projected with low dependence from ab initio wave functions, it is shown here that the 6-31G(d,p) basis sets characterized the secondary interaction in geometrical point of view, as well as by means of the AIM protocol through the specific calculation of bond critical points between the fluoride and the axial hydrogen atoms.
A theoretical investigation about the cooperative effect on ( HCN )n homo and ( HCN )n ⋯ HF heterochains was performed in terms of structural parameters and topological properties obtained in concordance with the protocol of Bader's atoms in molecules theory. Initially, the hydrogen bonding distances, electronic densities, and Laplacian descriptors were used to characterize small ( HCN )n and ( HCN )n ⋯ HF chains formed by n = 2–4 units of HCN . Hydrogen bond distances and distribution of charge density have revealed that the cooperative effect on ( HCN )n ⋯ HF heterochains is ruled by the polarity of the extreme hydrofluoric acid species. Furthermore, we investigated larger homo and heterochain systems formed by n = 2–8 molecules of HCN . In this insight, the drastic polarized effect caused by HF molecule which was considered very substantial at prior, in fact is seriously limited by an excessive number of HCN molecules connected to the heterochain. This leads to a stabilization of the ( N ⋯ HF ) hydrogen bonds with invariable electronic density in the range of [Formula: see text]. In this stage and henceforth, the cooperative effect is re-established with n = 4 molecules of HCN . Thereby, the electronic density of the hydrogen bonds become unaltered within the ( HCN )n ⋯ HF heterochains.
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