Estimations of energy of noncovalent bonding from integrals over interatomic zero‐flux surfaces: Correlation trends and beyond

Abstract

Bonding energies of 50 associates composed by neutral molecules (atoms) and bounded by various weak noncovalent interactions are calculated within the DFT framework using the PBE0/aug-cc-pVTZ combination. The electronic virial and electron density values at bond critical points together with their integrals over interatomic surfaces are tested to check their ability to estimate bonding energies. Two correlations schemes dealing with integrals over interatomic surface are suggested to estimate bonding energy of any noncovalent interaction. The physical meaning of explored and several known correlations is discussed. Methods to estimate interatomic surface integrals of electronic virial and electron density are proposed. © 2018 Wiley Periodicals, Inc.

Assembly of Tetrazolylfuroxan Organic Salts: Multipurpose Green Energetic Materials with High Enthalpies of Formation and Excellent Detonation Performance

“…Although the QTAIM approach showst hat there is an oncovalenti nteraction between azido and tetrazolyl moieties in the isolatedd enser DUQGUT anion ( Figure S5), this changeo fa tomic connectivity does not significantly increaset he density of azido, tetrazolyl, and furoxan motifs. Namely,t he larger difference between the density of chemicalf unctions in the isolateda nions from DUQGUT and 8·H 2 Os tructures is observed for the azido group and it is nearly meaningless,0 .0002 gcm À3 .M oreover,t his noncovalent interaction in DUQGUT is repulsive in terms of the interacting quantum atoms approach [27] (Figure S5) or,a tl east, very weak ( % 1kcal mol À1 )a ccording to the correlation of the interatomic surfacei ntegral of electron density [28] and nondirectional( ellipticity of electron density [29] at bond critical point equals 0.99), which makes it highly likely to be affected by vibrational smearing and/orsupramolecular association. [10e, 30] The physical and detonation properties, such as thermal stability,d ensity,e nthalpy of formation, detonation performance, as well as sensitivity of all the compounds, were investigated.…”

“…Namely, the larger difference between the density of chemical functions in the isolated anions from DUQGUT and 8⋅ H 2 O structures is observed for the azido group and it is nearly meaningless, 0.0002 g cm −3 . Moreover, this noncovalent interaction in DUQGUT is repulsive in terms of the interacting quantum atoms approach (Figure S5) or, at least, very weak (≈1 kcal mol −1 ) according to the correlation of the interatomic surface integral of electron density and nondirectional (ellipticity of electron density at bond critical point equals 0.99), which makes it highly likely to be affected by vibrational smearing and/or supramolecular association …”

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.…”

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.…”