Chalcogen Noncovalent Interactions between Diazines and Sulfur Oxides in Supramolecular Circular Chains DOI Open Access
Emna Rahali, Zahra Noori, Youssef Arfaoui

et al.

International Journal of Molecular Sciences, Journal Year: 2024, Volume and Issue: 25(13), P. 7497 - 7497

Published: July 8, 2024

The noncovalent chalcogen interaction between SO2/SO3 and diazines was studied through a dispersion-corrected DFT Kohn-Sham molecular orbital together with quantitative energy decomposition analyses. For this, supramolecular circular chains of up to 12 molecules were built the aim checking capability diazine detect compounds within atmosphere. Trends in energies increasing number are mainly determined by Pauli steric repulsion involved these σ-hole/π-hole interactions. But more importantly, despite assumed electrostatic nature interactions, covalent component also plays determinant role its strength bonds. Noticeably, π-hole interactions supported charge transfer from molecules. Interaction complexes not only S···N bond lengths but attractive determine trends. These results should allow us establish fundamental characteristics bonding based on nature, which is relevance for capture sulfur oxides.

Language: Английский

The borderless world of chemical bonding across the van der Waals crust and the valence region DOI Creative Commons
Jorge Echeverría, Santiago Álvarez

Chemical Science, Journal Year: 2023, Volume and Issue: 14(42), P. 11647 - 11688

Published: Jan. 1, 2023

The definition of the van der Waals crust as spherical section between atomic radius and an element is discussed a survey application penetration index two interacting atoms in wide variety covalent, polar, coordinative or noncovalent bonding situations presented. It shown that this newly defined parameter permits comparison pairs structural computational studies independently atom sizes.

Language: Английский

Citations

30
Energy Decomposition Analysis for excited states: An Extension based on TDDFT DOI Creative Commons
Florian Kreuter, Ralf Tonner

Physical Chemistry Chemical Physics, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Energy decomposition analysis (EDA) is extended by the excited state EDA (exc-EDA) using time-dependent density functional theory (TDDFT). Validated through studies on exciplexes, it demonstrates utility singlet fission in pentacene.

Language: Английский

Citations

1
A new look at the chalcogen bond: π-hole-based chalcogen (Se, Te) bonding which does not include a σ-hole interaction DOI
Eugene A. Katlenok, Maxim L. Kuznetsov, Nikolay A. Semenov

et al.

Inorganic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(10), P. 3065 - 3081

Published: Jan. 1, 2023

Chalcogen bonding which does not include σ-hole interaction.

Language: Английский

Citations

17
Understanding chemistry with thesymmetry‐decomposed Voronoideformation density charge analysis DOI Creative Commons
Celine Nieuwland, Pascal Vermeeren, F. Matthias Bickelhaupt

et al.

Journal of Computational Chemistry, Journal Year: 2023, Volume and Issue: 44(27), P. 2108 - 2119

Published: July 5, 2023

Abstract The symmetry‐decomposed Voronoi deformation density (VDD) charge analysis is an insightful and robust computational tool to aid the understanding of chemical bonding throughout all fields chemistry. This method quantifies atomic flow associated with chemical‐bond formation enables decomposition this into contributions (1) orbital interaction types, that is, Pauli repulsive or interactions; (2) per irreducible representation (irrep) any point‐group symmetry interacting closed‐shell molecular fragments; now also (3) open‐shell (i.e., radical) fragments. VDD augments energy (EDA) so repulsion interactions can be quantified both atom irrep, for example, σ, π, δ electrons. provides detailed insights fundamental aspects are not accessible from EDA.

Language: Английский

Citations

17
Anion transporters based on halogen, chalcogen, and pnictogen bonds: towards biological applications DOI Creative Commons
Anurag Singh, Aarón Torres‐Huerta, F. Meyer

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(37), P. 15006 - 15022

Published: Jan. 1, 2024

Synthetic anion receptors based on sigma-hole interactions are increasingly used to transport anions across membranes. This article discusses the progress in field and prospects for biological applications.

Language: Английский

Citations

7
Acidity of Isomorphic Substituted Zeolites with B, Al and Ga Revisited DOI
André Nicolai Petelski, Nélida M. Peruchena, María Fernanda Zalazar

et al.

ChemPhysChem, Journal Year: 2024, Volume and Issue: 25(9)

Published: Feb. 14, 2024

Abstract Isomorphic substitution of zeolites with B, Al and Ga is a widely used approach in catalysis. The experimentally reported trend their acidities decreases the order: Al>Ga>B. However, consistent explanation still lacking literature. To bring more understanding this trend, density functional theory computations were conducted on several model systems. First, acidity small clusters two (2T) five (5T) tetrahedral sites was analyzed. These systems then projected onto three large void structures: H‐[A]‐BEA (52T), H‐[A]‐FAU (84T) H‐[A]‐MOR (112T) A=B, Al, Ga. Our electron Interacting Quantum Atom analyses show that originates from much stronger O−Al bond, which dominated by electrostatic attraction. bridging hydroxyl therefore donates charge to metal, proton becomes positive consequently acidic. are acidic than B due greater covalent nature O−Ga bond. resulting acidity, as seen ammonia, depends both oxygen distribution surrounding oxygens exerted substituents.

Language: Английский

Citations

5
Energy decomposition analysis method using density matrix formulation DOI Creative Commons

Yueyang Zhang,

L. Yan, Wei Wu

et al.

The Journal of Chemical Physics, Journal Year: 2024, Volume and Issue: 160(17)

Published: May 1, 2024

In this work, an energy decomposition analysis (EDA) method with the strategy of density matrix, called DM-EDA, is proposed on basis single reference electronic structure calculations. Different from traditional EDA methods, instead intermediate state wave function, terms in DM-EDA are expressed forms matrix. This can be carried out various kinds matrices. With efficient implementation, not only greatly improves computational efficiency but also provides quantitative knowledge intermolecular interactions a large number monomers.

Language: Английский

Citations

5
“Hydridic Hydrogen-Bond Donors” Are Not Hydrogen-Bond Donors DOI Creative Commons
Lucas de Azevedo Santos, Pascal Vermeeren, F. Matthias Bickelhaupt

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(37), P. 25701 - 25709

Published: Sept. 3, 2024

Herein, we dismiss a recent proposal by Civiš, Hobza, and co-workers to modify the IUPAC definition of hydrogen bonds in order expand scope from protonic Y-H

Language: Английский

Citations

5
Origin of the Bürgi‐Dunitz Angle DOI Creative Commons
Humberto A. Rodríguez, F. Matthias Bickelhaupt, Israel Fernández

et al.

ChemPhysChem, Journal Year: 2023, Volume and Issue: 24(17)

Published: June 12, 2023

The Bürgi-Dunitz (BD) angle plays a pivotal role in organic chemistry to rationalize the nucleophilic addition carbonyl groups. Yet, origin of obtuse trajectory nucleophile remains incompletely understood. Herein, we quantify importance underlying physical factors quantum chemically. BD appears originate from concerted action reduced Pauli repulsion between HOMO and π bond, more stabilizing HOMO-π*-LUMO(C=O) interaction, as well favorable electrostatic attraction.

Language: Английский

Citations

12
Pnictogen bond‐driven control of the molecular interaction between organophosphorus and acetylcholinesterase enzyme DOI Creative Commons
Gustavo A. Andolpho, Teodorico C. Ramalho

Journal of Computational Chemistry, Journal Year: 2024, Volume and Issue: 45(15), P. 1303 - 1315

Published: Feb. 16, 2024

Abstract This study addresses a comprehensive assessment of the interaction between chemical warfare agents (CWA) and acetylcholinesterase (AChE) systems, focus on intriguing pnictogen‐bond (PnB). Utilizing crystallographic data from Protein Data Bank pertaining to AChE‐CWA complex involving Sarin (GB), Cyclosarin (GF), 2‐[fluoro(methyl)phosphoryl]oxy‐1,1‐dimethylcyclopentane (GP) venomous agent X (VX) agents, CWA is systematically displaced by increments 0.1 Å along PO bond axis, extending its distance 4 original position. The AIM analysis was carried out consistently revealed presence significant bond. Investigating intrinsic nature PnB, NBO EDA unearthed contribution orbital factors overall energy system. Strikingly, this observation challenges conventional σ‐hole explanation commonly associated with such interactions. finding adds layer complexity understanding encouraging further exploration into underlying mechanisms governing these phenomena.

Language: Английский

Citations

4