The use of electrostatic potential at nuclei in the analysis of halogen bonding

Abstract

The molecular electrostatic potential (MESP) at the nuclei of a large heterogeneous set of halogen bonded complexes calculated at M06-2X/aug-cc-pVTZ level of theory, is studied. The halogen bond formation leads...

Molecular Electrostatic Potential Topology Analysis of Noncovalent Interactions

“…The ΔΔ V n showed a good linear correlation with the noncovalent interaction energy, E int (Figure ). A recent study confirmed that the strength of even very weakly halogen-bonded systems can be explained in terms of the subtle fluctuation that occurs in the MESP at closely interacting atoms . This study also showed that, in contrast to MESP surface analysis, MESP topological analysis of halogen bonding is more reliable and accurate.…”

“…A recent study confirmed that the strength of even very weakly halogenbonded systems can be explained in terms of the subtle fluctuation that occurs in the MESP at closely interacting atoms. 49 This study also showed that, in contrast to MESP surface analysis, MESP topological analysis of halogen bonding is more reliable and accurate. The ΔΔV n versus E int correlation unifies hydrogen-bonded and other noncovalently bonded complexes to a single category, the eDA complex.…”

“…The MESP at the nucleus “A” of a molecule ( V n ) is derived by excluding the nuclear contribution due to Z A from the definition of MESP, which can be expressed as where Z A is the charge on nucleus A with radius vector R A , Z B and R B are the charge and position of nucleus B, r' is a dummy integration variable, and ρ­( r′ ) is the electronic density function of the corresponding molecule. Even for minor changes in the ρ­( r ) distribution, V n exhibits corresponding observable alterations. ,− For instance, the V n of the oxygen that serves as an electron donor in the methanol dimer is 16.5 kcal/mol less negative than the monomer, whereas the other oxygen becomes 17.2 kcal/mol more negative. The change in V n at the interacting atoms ((Δ V n ) has been used to evaluate the donor–acceptor feature of noncovalent interactions in a variety of chemical systems (Figure ).…”

Interplay of Hydrogen, Pnicogen, and Chalcogen Bonding in X(H2O)n=1–5 (X = NO, NO+, and NO–) Complexes: Energetics Insights via a Molecular Tailoring Approach

“…The positions of V min and V max are marked in Figure . During the complex formation between X and H 2 O, there is a change in corresponding MESP maxima and minima, and the magnitude of these MESP changes are designated as Δ V max and Δ V min , respectively. , Thus, Δ V max = V max_iso – V max_com , where V max_iso and V max_com are V max located on a particular site of isolated species and its interacted complex, respectively. Similarly, we can define Δ V min , and its magnitude is a rough estimate of the change in the electron density during complex formation.…”

How Do Small Differences in Geometries Affect Electrostatic Potentials of High-Energy Molecules? Critical News from Critical Points

“…For nitroaromatic explosives, values of positive potential at the critical points (CPs) located above the aromatic rings could be used to assess trends in sensitivity toward detonation. Critical points represent the most electron-rich (V min ) or electron-depleted (V max ) sites of the molecular electrostatic potential [13]. It is important to point out that molecular electrostatic potential is the physical characteristic of a molecule which could be both experimentally determined and calculated by ab initio calculations.…”