A Universal Quantitative Descriptor of the Dispersion Interaction Potential

Abstract

London dispersion, universally attractive forces originating from fluctuating dipoles,i so mnipresent in molecules.W hile its understanding has recently made tremendous progress,i ts general appreciation is still lagging behind electrostatics.T his can be explained by the simple tools available to study electrostatic interactions,such as electrostatic potential (ESP) maps and partial charges,a nd al ackt hereof for dispersion. We herein report au niversal quantitative descriptor of dispersion interaction potentials,w hicha llows assessing dispersion visually by London dispersion potential (LDP) maps,and quantitatively using the average LDP on the van der Waals surface.W edemonstrate the utility of these new tools by constructing aq uantitative dispersion energy scale of the elements and common substituents,s tudying non-covalent interactions (NCIs), and developing modern linear free energy relationships in catalysis.

Quantifying Interactions and Solvent Effects Using Molecular Balances and Model Complexes

“…Overall, the findings supported other theoretical indications that direct metal-metal interactions in closed-shell complexes are minor compared to those occurring between the ligands. [58][59][60] Electron Delocalization in "Non-covalent" Interactions…”

Simple and efficient visualization of aromaticity: bond currents calculated from NICS values

“…1, we demonstrate the various numerical and visual aromaticity evaluators for anthracene (CC7, Scheme 2). We note that, in general, there is a continued interest in visualizing abstract chemical phenomena, as is demonstrated by the recent publications detailing such methods for, e.g., dispersion forces, 25 strain 26 and Clar sextets in polybenzenoid hydrocarbons. 27 In the study of aromaticity, despite the clear advantages of pictorial depiction, p-electron current density visualization methods are not the most widely used.…”

Machine learning activation energies of chemical reactions

“…Electronic properties of the reactants and TSs were calculated with the B3LYP/6‐31+G(d) level of theory and used as features for the models. Reactant features were ionization energies; electron attachment energies 222 ; the surface electrostatic potential and electrostatic potentials at reactive nuclei 223,224 ; local and global descriptors of nucleophilicity and electrophilicity 225 ; atomic charges; bond orders; solvent accessible surface areas 226 ; and a descriptor for dispersion 227 . TS features were the activation barrier of the reaction as calculated with the ωB97X‐D/6‐311+G(d,p) level of theory; TS atomic charges; TS bond orders; and TS nuclear electrostatic potentials.…”