Evaluation of Electron Density Shifts in Noncovalent Interactions.

Iñigo Iribarren,Cristina Trujillo,Goar Sánchez-Sanz,Ibon Alkorta,José Elguero

doi:10.1021/acs.jpca.1c00830

Abstract

In the present paper, we report the quantitative evaluation of the electron density shift (EDS) maps within different complexes. Values associated with the total EDS maps exhibited good correlation with different quantities such as interaction energies, Eint, intermolecular distances, bond critical points, and LMOEDA energy decomposition terms. Besides, EDS maps at different cutoffs were also evaluated and related with the interaction energies values. Finally, EDS maps and their corresponding values are found to correlate with Eint within systems with cooperative effects. To our knowledge, this is the first time that the EDS has been quanitatively evaluated.

Highlights

Noncovalent interactions are of utmost importance across all domains, from chemistry to biology
A number of new noncovalent interactions have been described.[8]. Their naming is derived from the periodic table column associated with the Lewis acid atoms involved in the interaction: halogen,[9−14] chalcogen,[15−21] pnicogen,[22−29] tetrel,[20,30−34] triel,[35,36] spodium,[37] regium,[38−42] alkali-earth,[43,44] and alkali[45] bonds correspond to the interaction between an electron donor group and an atom in the Lewis acid that belongs to columns 16−11, 2 and 1 of the periodic table, respectively
The electron density shift (EDS) maps concomitantly with their corresponding values provide a qualitative and quantitative tool to analyze a wide variety of interactions

Summary

Introduction

Noncovalent interactions are of utmost importance across all domains, from chemistry to biology. The most important and best studied interaction is the hydrogen bond (HB).[1−5] HB corresponds to the attractive interaction between a hydrogen atom (from a molecule or molecular fragment X−H, where X is more electronegative than H), and an atom within the same (intramolecular) or different (intermolecular) molecule.[6] The second most important interaction is the halogen bond that was included by Mulliken in their theory of electron donor− acceptor complexes in the 1950s.7. It is worth noting that, in several cases, interaction energies suffer from collateral effects such as electronic repulsion, and competitive interactions that can obfuscate the estimation of the noncovalent interaction strength

Methods

Results

Conclusion