Theoretical Study of Fe³⁺ and Ni²⁺ Ion Interactions in Ethaline as the Deep Eutectic Solvent and Water Solutions Using Molecular Dynamics, Quantum Theory of Atoms in Molecules, and Non-Covalent Interactions

ACS Omega, Journal Year: 2025, Volume and Issue: 10(16), P. 16015 - 16030

Published: April 16, 2025

Deep eutectic solvents (DES) have several advantages compared to water and traditional solvents, making them an alternative, especially in applications that require better solvation, greater thermal stability, a lower environmental impact. This study aimed analyze the behavior of Fe3+ Ni2+ ions two quantities (300 5580 molecules) solvent based on choline chloride ethylene glycol (1ChCl:2EG). The computational methods used involved molecular dynamics, quantum theory atoms molecules (QTAIM), noncovalent interactions simulations. Analysis radial distribution function multiplied by number density [g(r)ρ] cumulative (CN) indicated between metal were strongest for systems with most water. QTAIM determined bond critical point, electron [ρ(r)], Laplacian electronic [∇2ρ(r)], localization (η, ELF), allowing be analyzed. Polarizability both ethaline was compared; increasing order polarizability < Fe2+, being least polarizable due its high charge smaller ionic radius. In mixed Fe2+ or added Ni2+, species same competed similarly DES. intermolecular forces DES are weaker solvent's polarity dielectric constant than highest content (5580 molecules), surrounded largest molecules, followed Ni2+. These results may help understand solvation these different media, which has implications use electrodeposition, batteries, corrosion inhibition.

Language: Английский

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Decorated crown ethers as selective ion traps: Solvent’s role in crown’s preference towards a specific ion

Journal of Molecular Liquids, Journal Year: 2023, Volume and Issue: 381, P. 121791 - 121791

Published: April 6, 2023

Language: Английский

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Application of Recurrence Plot Analysis to Examine Dynamics of Biological Molecules on the Example of Aggregation of Seed Mucilage Components

Entropy, Journal Year: 2024, Volume and Issue: 26(5), P. 380 - 380

Published: April 29, 2024

The goal of the research is to describe aggregation process inside mucilage produced by plant seeds using molecular dynamics (MD) combined with time series algorithmic analysis based on recurrence plots. studied biological molecules model seed composed three main polysaccharides, i.e. pectins, hemicellulose, and cellulose. modeling assumption that a classical–quantum passage underlies in mucilage, resulting from non-covalent interactions, as they affect macroscopic properties system. applied plot approach an important tool for data mining dedicated analyzing originating complex, chaotic systems. In current research, we demonstrated advanced can reveal some features system, namely temperature-dependent regions different increments number hydrogen bonds stable oscillation hydrophobic–polar interactions. Henceforth, pave path automatic data-mining methods intermediate step application analysis, generalization applications other (biological molecules) datasets straightforward.

Language: Английский

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Force Decomposition Analysis: A Method to Decompose Intermolecular Forces into Physically Relevant Component Contributions

The Journal of Physical Chemistry A, Journal Year: 2023, Volume and Issue: 127(7), P. 1760 - 1774

Published: Feb. 8, 2023

Computational quantum chemistry can be more than just numerical experiments when methods are specifically adapted to investigate chemical concepts. One important example is the development of energy decomposition analysis (EDA) reveal physical driving forces behind intermolecular interactions. In EDA, typically interaction from a good-quality density functional theory (DFT) calculation decomposed into multiple additive components that unveil permanent and induced electrostatics, Pauli repulsion, dispersion, charge-transfer contributions noncovalent Herein, we formulate, implement, decomposing associated with interactions same components. The resulting force (FDA) potentially useful as complement EDA understand chemistry, while also providing far information an for data purposes such training physics-based fields. We apply FDA based on absolutely localized molecular orbitals (ALMOs) analyze water sodium chloride ions well in dimer. responsible geometric changes carbon dioxide upon adsorption onto (and activation by) gold silver anions. how EDA-based field clusters, namely MB-UCB, compare those analysis.

Language: Английский

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Application of the FFLUX Force Field to Molecular Crystals: A Study of Formamide

Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(21), P. 7946 - 7959

Published: Oct. 17, 2023

In this work, we present the first application of quantum chemical topology force field FFLUX to solid state. utilizes Gaussian process regression machine learning models trained on data from interacting atom partitioning scheme predict atomic energies and flexible multipole moments that change with geometry. Here, ambient (α) high-pressure (β) polymorphs formamide are used as test systems optimized using FFLUX. Optimizing structures increasing multipolar ranks indicates lattice parameters α phase differ by less than 5% experimental structure when up quadrupole used. These differences found be in line dispersion-corrected density functional theory. Lattice dynamics calculations also possible FFLUX, yielding harmonic phonon spectra comparable DFT while enabling larger supercells considered is typically first-principles calculations. promising results indicate can accurately determine properties molecular solids difficult access DFT, including structural dynamics, free energies, at finite temperature.

Language: Английский

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Anions as Lewis Acids in Noncovalent Bonds

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: July 8, 2024

The ability of an anion to serve as electron-accepting Lewis acid in a noncovalent bond is assessed via DFT calculations. NH

Language: Английский

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Weakly bound mercury-noble gas adducts: Strength, range and nature of the interaction, spectroscopic and thermodynamical properties

Computational and Theoretical Chemistry, Journal Year: 2024, Volume and Issue: 1239, P. 114797 - 114797

Published: Aug. 7, 2024

Language: Английский

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Probing Non-Covalent Interactions through Molecular Balances: A REG-IQA Study

Molecules, Journal Year: 2024, Volume and Issue: 29(5), P. 1043 - 1043

Published: Feb. 28, 2024

The interaction energies of two series molecular balances (1-X with X = H, Me, OMe, NMe2 and 2-Y Y CN, NO2, NMe2) designed to probe carbonyl…carbonyl interactions were analysed at the B3LYP/6-311++G(d,p)-D3 level theory using energy partitioning method Interacting Quantum Atoms/Fragments (IQA/IQF). partitioned are by Relative Energy Gradient (REG) method, which calculates correlation between these total a system, thereby explaining role atoms have in energetic behaviour system. traditional “back-of-the-envelope” open closed conformations do not correspond those lowest energy. Hence, more care needs be taken when considering geometries use for comparison experiment. REG-IQA shows that 1-H 1-OMe behave differently 1-Me 1-NMe2 because latter show prominent electrostatics carbonyl groups undergoes larger dihedral rotation due bulkiness functional groups. For balance, same across as balances. From an atomistic point view, formation conformer is favoured polarisation charge-transfer effects on amide bond all counterbalanced de-pyramidalisation nitrogen. Moreover, focusing oxygen α-carbon remaining group, major conformer, goes against well-known n-π* orbital overlap concept. However, REG-IQF exchange–correlation overtake working fragments around groups, while they act par 1-NMe2. also balance correlated inductive electron-donating -withdrawing trends aromatic We demonstrate methods such REG-IQA/IQF can help fine-tuning prior experiment govern probed highly dependent involved.

Language: Английский

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Alkali Metal-Ion Binding by a Model Macrocycle Containing a C-I···N Halogen Bonded Network: A DFT Study of C-I···M+ and N···M+ Binding Interactions, M+ = Li+, Na+, K+, and Rb+

Inorganics, Journal Year: 2024, Volume and Issue: 12(6), P. 161 - 161

Published: June 6, 2024

The complexation of an alkali metal ion by a model macrocycle is examined using the M05-2X/DGDZVP DFT method. built connecting three cyclopenta[b]pyrrole motifs with alternating acetylene and ethylene linkages. Replacing one C-H bonds in each motif C-I bond allows for formation intramolecular C-I···N halogen bonds. Two distinct binding modes were found ion. In mode, occurs solely iodine atoms, via I···M+ interactions, while maintaining integrity energies are range −66 to −35 kcal/mol. other includes nitrogen atom as well, −71 −38 this network weakened. presence strength interactions further AIM NBO calculations. Lastly, geometries transition state structures linking less stable more complexes obtained, their calculated Gibbs free energy barriers 1.6 1.9

Language: Английский

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

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

Published: Nov. 16, 2023

Telluronium salts [Ar

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