Density functional theory for van der Waals complexes: Size matters DOI Creative Commons
Montgomery Gray, John M. Herbert

Published: Nov. 7, 2023

Over the past 25 years there has been remarkable progress towards accurate description of nonbonded interactions within context density functional theory (DFT). Various methods have devised to capture London dispersion, which is most exacting contribution noncovalent interactions; these strategies include both new functionals as well ad hoc dispersion corrections existing functionals. At present, it possible compute interaction energies for small van der Waals complexes (containing ~20 atoms) an accuracy ~0.5 kcal/mol, using a range dispersion-inclusive DFT that are reviewed here. Systematic tests reveal consistency across different methods, at least dimers, although magnitude systematically smaller than benchmark because some resides semilocal exchange-correlation functional, in manner difficult disentangle. Despite impressive results systems, best contemporary afford larger errors systems with 50-130 atoms, approaching 3-5 kcal/mol compared ab initio benchmarks total energies, uncertainties this size. Errors vary widely from one method next ,with no discernible systematic trend. Nanoscale thus represent frontier development interactions.

Language: Английский

Density functional theory for van der Waals complexes: Size matters DOI
Montgomery Gray, John M. Herbert

Annual reports in computational chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 1 - 61

Published: Jan. 1, 2024

Language: Английский

Citations

10
Definition of the Halogen Bond (IUPAC Recommendations 2013): A Revisit DOI
Pradeep R. Varadwaj, Arpita Varadwaj, Helder M. Marques

et al.

Crystal Growth & Design, Journal Year: 2024, Volume and Issue: 24(13), P. 5494 - 5525

Published: June 24, 2024

This Article revisits the "Definition of Halogen Bond (IUPAC Recommendations 2013)" [Desiraju, G. R. Pure Appl. Chem. 2013, 85 (8), 1711–1713], recommendations that fail to include fundamental, underlying concept (electrophilic) σ- and p-/π-hole theory orbital-based charge transfer interactions accompany halogen bond formation. An electrophilic σ-hole, or p-/π-hole, is an electron-density-deficient region positive polarity (and potential) on electrostatic surface side along, orthogonal to, a covalently bonded in molecular entity leads development noncovalent interaction─a bond─when close proximity electron-density-rich nucleophilic same another identical different entity, with which it interacts. re-examines characteristic features lists wide variety donors acceptors participate bonding. We add caveats are essential for identifying bonding chemical systems, necessary appropriate use terminologies involved. Illustrative examples systems feature inter- intramolecular bonds other crystalline phase given, together case study some dimer using first-principles calculations. also point out π-hole/belt (or p-hole/belt) may develop derivative halogenated molecules be prone forming when nucleophiles similar entity.

Language: Английский

Citations

10
Formulating Reduced Density Gradient Approaches for Noncovalent Interactions DOI
Cristian Guerra, José Luis Burgos, Leandro Ayarde‐Henríquez

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: 128(30), P. 6158 - 6166

Published: July 23, 2024

This work elucidates several forms of reduced electron density gradient (RDG) to describe noncovalent interactions (NCIs). By interpreting the RDG as a local moment function, we systematically leveraged Weizacker's and Fermi's moments. resulted in high-fidelity representations consistent with NCI analysis. In addition, version derived from Lagrangian kinetic energy is conveniently normalized. These results suggest nonexistence particular formulation when performing Thus, an in-depth examination theoretical foundations connecting function nature necessary.

Language: Английский

Citations

6
Density functional theory for van der Waals complexes: Size matters DOI Creative Commons
Montgomery Gray, John M. Herbert

Published: Feb. 7, 2024

Over the past 25 years there has been remarkable progress towards accurate description of nonbonded interactions within context density functional theory (DFT). Various methods have devised to capture London dispersion, which is most exacting contribution noncovalent interactions; these strategies include both new functionals as well ad hoc dispersion corrections existing functionals. At present, it possible compute interaction energies for small van der Waals complexes (containing ~20 atoms) an accuracy ~0.5 kcal/mol, using a range dispersion-inclusive DFT that are reviewed here. Systematic tests reveal consistency across different methods, at least dimers. same time, magnitude systematically smaller than benchmark because some resides semilocal exchange-correlation functional, in manner difficult disentangle. Despite impressive results systems, best contemporary afford larger errors systems with >~ 100 atoms, approaching 3-5 kcal/mol compared ab initio benchmarks total energies, although themselves uncertainties this size. Errors vary widely from one method next, no discernible systematic trend. Nanoscale thus represent frontier development interactions.

Language: Английский

Citations

4
Dispersion Control over Molecule Cohesion: Exploiting and Dissecting the Tipping Power of Aromatic Rings DOI Creative Commons
Ricardo A. Mata,

Tlektes Zhanabekova,

Daniel A. Obenchain

et al.

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(8), P. 1077 - 1086

Published: March 27, 2024

ConspectusWe have learned over the past years how London dispersion forces can be effectively used to influence or even qualitatively tip structure of aggregates and conformation single molecules. This happens despite fact that contacts are much weaker than competing polar forces. It is a classical case strength by numbers, with importance scaling system size. Knowledge about tipping points, however difficult attain, necessary for rational design intermolecular One requires careful assessment interactions, either sensitive spectroscopic techniques study isolated molecules theoretical approaches. Of particular interest systems close point, when interactions barely outweigh approach other interactions. Such subtle cases important milestones scale-up realistic multi-interaction situations encountered in fields life materials science. In searching examples provide ideal complexes small clusters, aromatic offer diverse set variation electrostatic control dominant peripheral Our combined investigations valuable insights into balance because they typically allow us switch substituent on off. High-resolution rotational spectroscopy serves as benchmark molecular structures, correct calculations should based geometries. When discussing competition noncovalent obvious competitors directional hydrogen bonds. As second counterweight aryl we will discuss aurophilic/metallophilic which also strong stabilization number atoms involved. Vibrational most light atoms, OH bonds aggregate judged well stretching frequency. Experiments gas phase gauging accuracy quantum chemical predictions free solvent A tight collaboration utilizing these three methods allows experiment vs theory benchmarking overall structures energetics.

Language: Английский

Citations

4
Non-covalent interactions in binary mixtures of sulfamic acid and methylurea DOI
Utkirjon Holikulov, Аleksandr S. Kazachenko, Noureddine Issaoui

et al.

Journal of Molecular Liquids, Journal Year: 2025, Volume and Issue: unknown, P. 127788 - 127788

Published: May 1, 2025

Language: Английский

Citations

0
Sigma Hole Potentials as Tools: Quantifying and Partitioning Substituent Effects DOI Creative Commons
Kelling J. Donald,

Nam Pham,

Pranav Ravichandran

et al.

The Journal of Physical Chemistry A, Journal Year: 2023, Volume and Issue: 127(48), P. 10147 - 10158

Published: Nov. 21, 2023

Empirical substituent constants, such as the Hammett parameters, have found important utility in organic and other areas of chemistry. They are useful both predicting impact substitutions on chemical processes rationalizing after-the-fact observations bonding reactivity. We assess monoiodinated benzene rings find that modifications substituents induce electrostatic potentials at sigma hole terminal I center correlate strongly with established trends common substituents. As an alternative to experimental procedures involved obtaining empirically based computationally determined constants induced offer a model for quantifying influence mono- polyatomic, neutral, ionic their compounds. A partitioning scheme is proposed allows us discretely separate σ π contributions generate quantitative measures effects.

Language: Английский

Citations

8
Affinity of Telluronium Chalcogen Bond Donors for Lewis Bases in Solution: A Critical Experimental‐Theoretical Joint Study DOI Creative Commons

Loïc Groslambert,

Yann Cornaton, Matej Ditte

et al.

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 30(7)

Published: Nov. 16, 2023

Telluronium salts [Ar

Citations

5
Sigma Hole Supported Interactions: Qualitative Features, Various Incarnations, and Disputations DOI
Kelling J. Donald

Published: May 17, 2024

In a tour of the main group periodic table, we consider nature and impact induced positive potentials (sigma holes; σ-hole) on chemical bonding. The chapter moves rapidly from one column in table to next, following tendency that has emerged sigma hole interactions within (sub)groups based columns table. common features phenomenon as move next are emphasized. Distinctions, such substantial strengthening sigma-hole-type when region potential coincides with an empty p orbital perpendicular polarizing bonds (in groups 2 13, for example) highlighted. Many hole-type interactions, halogen bonds, easily recognized noncovalent even if charge transfer is not negligible. Other supported by holes largely coordinate covalent (dative) character. We point out persisting controversy about role different energy contributions bonding hole-supported while affirming some valuable insight concept affords us ways which it informing experimentalists motivating predictions new discoveries. Even agreement fundamental these weak, interest, engagement, possibilities understanding applications remarkably strong.

Language: Английский

Citations

1
Formulating reduced density gradient approaches for noncovalent interactions DOI Creative Commons
Cristian Guerra, José Luis Burgos, Leandro Ayarde‐Henríquez

et al.

Published: May 27, 2024

This work elucidates several forms of reduced electron density gradient (RDG) to describe non-covalent interactions (NCIs). By interpreting the RDG as a local-moment function, we systematically leveraged Weizacker's and Fermi's local moments. resulted in high-fidelity representations consistent with NCI analysis. In addition, version derived from Lagrangian kinetic energy is conveniently normalized. These results suggest non-existence particular formulation when performing Thus, an in-depth examination theoretical foundations connecting function nature necessary.

Language: Английский

Citations

1