Toward a Rigorous Definition of a Strength of Any Interaction Between Bader’s Atomic Basins

Abstract

Strength of interaction between Bader's atomic basins, enclosed by zero-flux surfaces of electron distribution, was proposed to be a measure of elastic deformation of an interaction. The set containing 53 atomic aggregate and covering all range of interaction strength (from van der Waals interactions to triple covalent bonds) was calculated by DFT and perturbation theory methods. Further analysis was performed to seek correlations between various local quantities based on electron density and effective force constants of stretching diatomic vibrations. The linear trend between effective force constants and the potential energy density at the (3, -1) critical point of electron distribution was found. This correlation was improved by the integration of the potential energy density over an interbasin zero-flux surface of electron density. Simple mechanical explanation of established trends is presented. The correlations can be further used to at least semiquantitatively compare any pair of interactions between Bader's atomic basins.

Can halogen bond energy be reliably estimated from electron density properties at bond critical point? The case of the (A)nZ—Y•••X−(X, Y = F, Cl, Br) interactions

“…Later, similar relationships were obtained and/or evaluated for other electron density based properties at BCP (eg, kinetic energy density, G b , Laplacian of the electron density, r 2 ρ b and the curvatures of the electron density distribution, λ || and λ ⊥ ) for various types of noncovalent interactions. [2,[13][14][15][16] Despite the EML formula (as any other similar relationships) was derived for the hydrogen bonds of a particular type, there were numerous attempts to apply the same equation for H-bonds of other types and even for other noncovalent interactions, among them halogen bonds. Meanwhile, such an expansion of the application of the EML formula is usually not justified.…”

Interplay of noncovalent interactions in antiseptic quaternary ammonium surfactant Miramistin

“…The (justified for weak interactions) relationship between the binding energy and the electronic potential energy density integrated over the corresponding interatomic zero-flux sur-faces (Ananyev et al, 2017;Romanova et al, 2018) gave a similar but somewhat smaller value of 2.3 kcal mol À1 . These points can be attributed to C-HÁ Á Á, C-HÁ Á ÁN and HÁ Á ÁH noncovalent interactions involving the arene ring.…”

“…The EML correlation (see above) gave the total energy of these interactions as 3.0 kcal mol À1 . The (justified for weak interactions) relationship between the binding energy and the electronic potential energy density integrated over the corresponding interatomic zero-flux sur-faces (Ananyev et al, 2017;Romanova et al, 2018) gave a similar but somewhat smaller value of 2.3 kcal mol À1 . We note that the relationship based on surface integral quantities usually provides more accurate results than the EML correlation: the corresponding r.m.s.…”

“…We note that the relationship based on surface integral quantities usually provides more accurate results than the EML correlation: the corresponding r.m.s. deviations are less than 1.0 (for different interaction types; Ananyev et al, 2017) and 1.7 kcal mol À1 (for hydrogen bonds only; Spackman, 2015).…”

Structure-directing sulfur...metal noncovalent semicoordination bonding

“…The most common real-space method, the Quantum Theory of Atoms in Molecules (QTAIM) (Matta & Boyd, 2007), provides an opportunity to explore bonding diatomic interactions with meaningful exchange energy contributions and subsequently to construct the atomic connectivity graph. The properties of corresponding descriptors of topological bonding, such as interatomic surfaces and (3, À1) critical points (CPs) of electron density (r), serve as weights of the connectivity graph and are frequently used to provide a range diatomic interactions in terms of charge separation and contributions to the energy of the system (Bader & Essé n, 1984;Cremer & Kraka, 1984;Silva Lopez & de Lera, 2011;Alkorta et al, 1998;Espinosa et al, 1998;Vener et al, 2012;Bartashevich, Matveychuk et al, 2014;Saleh et al, 2015;Lane et al, 2017;Ananyev et al, 2017;Borissova et al, 2008;Romanova et al, 2018). For instance, the topographic analysis of (r) in the transition metal complexes usually indicates the MÁ Á ÁX bonding interaction for any coordination bond, i.e.…”