Capture of CO<sub>2</sub> by Melamine Derivatives: A DFT Study Combining the Relative Energy Gradient Method with an Interaction Energy Partitioning Scheme

Ferrer, Maxime; Alkorta, Ibon; Elguero, Jose; Oliva-Enrich, Josep M.

doi:10.1021/acs.jpca.3c08412

Cited by 2 publications

(2 citation statements)

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“…5 ) indicates that the energy component can explain the overall profile and the value of REG provides its importance to explain it. A detailed description of this method is provided in the original article together with some applications [ 58 – 61 ], including a recent one that uses the energy decomposition scheme of Mandado et al [ 62 ] …”

Section: Methodsmentioning

confidence: 99%

“…The reaction coordinates have been analysed with Conceptual DFT (CDFT) tools. In addition, the strain/interaction model [ 52 – 55 ] coupled with the non-covalent interactions energy decomposition analysis (EDA-NCI) [ 56 , 57 ] have been analysed with the relative energy gradient (REG) method [ 58 – 62 ] to determine the most important energy contributions to the barriers.…”

Section: Introductionmentioning

confidence: 99%

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Understanding the coupling of non-metallic heteroatoms to CO2 from a Conceptual DFT perspective

Ferrer,

Elguero,

Alkorta

et al. 2024

J Mol Model

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Context A Conceptual DFT (CDFT) study has been carry out to analyse the coupling reactions of the simplest amine (CH3NH2), alcohol (CH3OH), and thiol (CH3SH) compounds with CO2 to form the corresponding adducts CH3NHCO2H, CH3OCO2H, and CH3SCO2H. The reaction mechanism takes place in a single step comprising two chemical events: nucleophilic attack of the non-metallic heteroatoms to CO2 followed by hydrogen atom transfer (HAT). According to our calculations, the participation of an additional nucleophilic molecule as HAT assistant entails important decreases in activation electronic energies. In such cases, the formation of a six-membered ring in the transition state (TS) reduces the angular stress with respect to the non-assisted paths, characterised by four-membered ring TSs. Through the analysis of the energy and reaction force profiles along the intrinsic reaction coordinate (IRC), the ratio of structural reorganisation and electronic rearrangement for both activation and relaxation energies has been computed. In addition, the analysis of the electronic chemical potential and reaction electronic flux profiles confirms that the highest electronic activity as well as their changes take place in the TS region. Finally, the distortion/interaction model using an energy decomposition scheme based on the electron density along the reaction coordinate has been carried out and the relative energy gradient (REG) method has been applied to identify the most important components associated to the barriers. Methods The theoretical calculation were performed with Gaussian-16 scientific program. The B3LYP-D3(BJ)/aug-cc-pVDZ level was used for optimization of the minima and TSs. IRC calculations has also been carried out connecting the TS with the associated minima. Conceptual-DFT (CDFT) calculations have been carried out with the Eyringpy program and in-house code. The distortion/interaction model along the reaction coordinate have used the decomposition scheme of Mandado et al. and the analysis of the importance of each components have been done with the relative energy gradient (REG) method.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Understanding the coupling of non-metallic heteroatoms to CO2 from a Conceptual DFT perspective

Ferrer,

Elguero,

Alkorta

et al. 2024

J Mol Model

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Probing Self‐Assembly of Ammeline in Chloroform and Aqueous Media: Interplay Between Hydrogen Bonding Diversity and Dimerization

Pamies,

Peruchena,

Petelski

2024

ChemPlusChem

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Ammeline (AM) is a molecule with a very low reputation in the field of supramolecular community, but with a recently proven potential both experimentally and theoretically. In this work, dispersion‐corrected density functional theory (DFT‐D) computations and molecular dynamics (MD) simulations were employed to understand the aggregation mechanism of AM in chloroform and water media. Our DFT‐D and MD analyzes show that the most important interactions are those formed by the amine groups (−NH2) with both the pyridine‐type nitrogen atoms and the carbonyl groups (C=O). In the more polar solvent, the interactions between water molecules and the C=O group prevent the AM from forming more interactions with itself. Nevertheless, four types of dimers involving N−H∙∙∙O interactions were found to exist in water solutions. The overlooked tetrel bond between endocyclic N and C atoms can also stabilize dimers in solution. Moreover, while most AM dimers are enthalpy‐driven, our results indicate that the unique DD‐AA dimer (D=donor, A=acceptor) that originates cyclic rosettes is entropy‐driven.

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Capture of CO₂ by Melamine Derivatives: A DFT Study Combining the Relative Energy Gradient Method with an Interaction Energy Partitioning Scheme

Cited by 2 publications

References 58 publications

Understanding the coupling of non-metallic heteroatoms to CO2 from a Conceptual DFT perspective

Understanding the coupling of non-metallic heteroatoms to CO2 from a Conceptual DFT perspective

Probing Self‐Assembly of Ammeline in Chloroform and Aqueous Media: Interplay Between Hydrogen Bonding Diversity and Dimerization

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Capture of CO2 by Melamine Derivatives: A DFT Study Combining the Relative Energy Gradient Method with an Interaction Energy Partitioning Scheme

Cited by 2 publications

References 58 publications

Understanding the coupling of non-metallic heteroatoms to CO2 from a Conceptual DFT perspective

Understanding the coupling of non-metallic heteroatoms to CO2 from a Conceptual DFT perspective

Probing Self‐Assembly of Ammeline in Chloroform and Aqueous Media: Interplay Between Hydrogen Bonding Diversity and Dimerization

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Product

Resources

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Capture of CO₂ by Melamine Derivatives: A DFT Study Combining the Relative Energy Gradient Method with an Interaction Energy Partitioning Scheme