The common trends for the halogen, chalcogen, and pnictogen bonds via sorting principles and local bonding properties

The explicit role of electron exchange in the hydrogen bonded molecular complexes

“…The first one was the bond critical point, BCP, a saddle point of the electron density, which indicates the presence of bonding between the atoms H and O w according to the QTAIM 37 . The second one was an inverted saddle point of the potential acting on an electron within a molecule, 57 PCP (maximum of the one‐dimensional PAEM potential barrier on the H∙∙∙O w line), which characterizes the strength of the atomic interaction 60,61,86 . The SF(DH) and SF(A) contributions to the electron density at BCP and PCP exhibit a proportional change for both isolated complexes and systems in aqueous solution (Figure 2, Tables S7 and S8).…”

“…68 The component F xc changes its direction in the HÁÁÁO w region similar to the F P (Figure 4 Figure 6), which characterize bonding in molecular systems. 60,61,86 However, neither v PAEM nor…”

“…37 The second one was an inverted saddle point of the potential acting on an electron within a molecule, 57 PCP (maximum of the one-dimensional PAEM potential barrier on the HÁÁÁO w line), which characterizes the strength of the atomic interaction. 60,61,86 The SF(DH) and SF(A) contributions to the electron density at BCP and PCP exhibit a proportional change for both isolated complexes and systems in aqueous solution (Figure 2, Tables S7 and S8). This is also observed for the H-bonds in the active sites of enzymes.…”

“…These noncovalent interactions have been intensively studied by various theoretical and experimental techniques 5–8 : ab initio calculations, 9,10 molecular dynamic modeling, 11 quantum mechanics/molecular mechanics calculations, 12 NMR and IR spectroscopy, 13–15 X‐Ray and neutron diffraction 16–18 and thermochemical experiments 19 . Among theoretical approaches, the electron density 7,20–23 and energy decomposition analyses 7,24 are gaining considerable popularity in the studies of H‐bonds in the isolated state, 25,26 solution 27 and solid state 28,29 . Lest us consider some of them shortly.…”

“…It reveals origins of selective binding in supramolecular systems, 53 helps to predict the stoichiometry of two-component crystals 54 and investigate the features of weak intermolecular interactions. 55,56 Recently the potential acting on an electron in a molecule PAEM 57 and Kohn-Sham effective potential, 58 which account for both electrostatic and exchangecorrelation effects, have also been used to identify the nature and strength of noncovalent interactions [59][60][61] and to classify them. 59 It provides insight into the preferred orientation for monomers in hydrogen, halogen and pnicogen bonded complexes.…”