Nitrogen-doped fullerenes for CO<sub>2</sub> capture: a DFT study

Anila, Sebastian; Suresh, Cherumuttathu H.

doi:10.1039/d2nj05761a

Cited by 5 publications

(7 citation statements)

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“…Also, on the basis of the energetics of interaction between polyanionic cyano-fullerides and CO 2 , the former systems have been proposed as promising candidates for CO 2 capture. Similarly, MESP analysis revealed the improved affinity of N-doped fullerenes as well as N-doped anionic modification of C 60 to CO 2 …”

Section: Other Applicationsmentioning

confidence: 94%

Molecular Electrostatic Potential Topology Analysis of Noncovalent Interactions

Suresh

Anila

2023

Acc. Chem. Res.

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Conspectus The topology of molecular electrostatic potential (MESP), V(r), derived from a reliable quantum chemical method has been used as a powerful tool for the study of intermolecular noncovalent interactions. The MESP topology mapping is achieved by computing both ∇V(r) data and the elements of the Hessian matrix at ∇V(r) = 0, the critical point. MESP minimum (V min) as well as MESP at a reaction center, specific to an atom (V n), have been employed as electronic parameters to interpret the variations in the reactivity (activation/deactivation) of chemical systems with respect to the influence of substituents, ligands, π-conjugation, aromaticity, trans influence, hybridization effects, steric effects, cooperativity, noncovalent interactions, etc. In this Account, several studies involving MESP topology analysis, which yielded interpretations of various noncovalent interactions and also provided new insights in the area of chemical bonding, are highlighted. The existence of lone pairs in molecules is distinctly reflected by the topology features of the MESP minima (V min). The V min is able to probe lone pairs in molecules, and it has been used as a reliable electronic parameter to assess their σ-donating power. Furthermore, MESP topology analysis can be used to forecast the structure and energetics of lone pair π-complexes. The MESP approach to rationalize lone pair interactions in molecular systems has led to the design of cyclic imines for CO2 capture. The MESP topology analysis of intermolecular complexes revealed a hitherto unknown phenomenon in chemical bonding theoryformation of a covalent bond due to the influence of a noncovalent bond. The MESP-guided approach to intermolecular interactions provided a successful design strategy for the development of CO2 capture systems. The MESP parameters V min and MESP at the nucleus, V n, derived for the molecular systems have been used as powerful measures for the extent of electron donor–acceptor (eDA) interactions in noncovalent complexes. Noncovalent bond formation leads to more negative MESP at the acceptor nucleus (V nA) and less negative MESP at the donor nucleus (V nD). The strong linear relationship observed between ΔΔV n = ΔV nD – ΔV nA and bond energy suggested that MESP data provide a clear evidence of bond formation. Furthermore, MESP topology studies established a cooperativity rule for understanding the donor–acceptor interactive behavior of a dimer D...A with a third molecule. According to this, the electron reorganization in the dimer due to the eDA interaction enhances electron richness at “A”, the acceptor, and enhances electron deficiency at “D”, the donor. Resultantly, D in D...A is more accepting toward trimer formation, while A in D...A is more donating. MESP topology offers promising design strategies to tune the electron-donating strength in various noncovalent interactions in hydrogen-, dihydrogen-, halogen-, tetrel-, pnicogen-, chalcogen-, and aerogen-bonded complexes and thereby to predict the interactive behavior of molecules. To sum...

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Section: Other Applicationsmentioning

confidence: 94%

Molecular Electrostatic Potential Topology Analysis of Noncovalent Interactions

Suresh

Anila

2023

Acc. Chem. Res.

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“…M06L is recognized as a robust DFT approach in terms of overall performance for the optimization of inorganic systems and studies of noncovalent interactions. [50][51][52] The MESP V(r) at a point r in the neighborhood of a molecular system is defined in Equation ( 1)…”

Section: Methodsmentioning

confidence: 99%

“…The density function theory (DFT) with the M06L procedure and 6‐311++G(d,p) basis set executed in Gaussian09 49 program package is used to optimize all the carbonyl ring molecules and their hydrogen bonded complexes used in the present study. M06L is recognized as a robust DFT approach in terms of overall performance for the optimization of inorganic systems and studies of noncovalent interactions 50–52 . The MESP V ( r ) at a point r in the neighborhood of a molecular system is defined in Equation ()

V (boldr) = \sum_{normalA}^{normalN} \frac{Z_{normalA}}{(||, boldr - R_{A})} - \int \frac{ρ ({boldr}^{'}) d^{3} {boldr}^{'}}{(||, boldr - r^{'})}

where Z A is the charge on nucleus A located at a distance R A , and ρ( rˈ ) is the molecule's continuous electronic density, and N is the total number of nuclei present in the molecular system.…”

Section: Methodsmentioning

confidence: 99%

Hydrogen bonds ofOCNHmotif in rings in drugs: A molecular electrostatic potential analysis

Haritha

Suresh

2023

J Comput Chem

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The OCNH unit is one of the most frequently encountered structural motifs in rings in drugs which serves dual role as the proton donor through NH bond and proton acceptor through the CO bond. Here, we predicted the HB strength (Eint) of OCNH motif with H2O for commonly observed 37 rings in drugs with DFT method M06L/6‐311++G(d,p). The HB strength is rationalized in terms of molecular electrostatic potential (MESP) topology parameters ΔVn(NH) and ΔVn(CO) which describe the relative electron deficient/rich nature of NH and CO, respectively, with respect to the reference formamide. The Eint of formamide is −10.0 kcal/mol whereas the Eint of ring systems is in the range −8.6 to −12.7 kcal/mol—a minor increase/decrease compared to the formamide. The variations in Eint are addressed using the MESP parameters ΔVn(NH) and ΔVn(CO) and proposed the hypothesis that a positive ΔVn(NH) enhances NH…Ow interaction while a negative ΔVn(CO) enhances the CO…Hw interaction. The hypothesis is proved by expressing Eint jointly as ΔVn(NH) and ΔVn(CO) and also verified for twenty FDA approved drugs. The predicted Eint for the drugs using ΔVn(NH) and ΔVn(CO) agreed well with the calculated Eint. The study confirms that even delicate variations in the electronic feature of a molecule can be quantified in terms of MESP parameters and they provide a priori prediction of the HB strength. The MESP topology analysis is recommended to understand the tunability of HB strength in drug motifs.

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“…The geometry optimizations were performed with a two-step process. The first step was performed using Hartree–Fock (HF) theory with a 3-21G basis set, and starting from the optimized geometry, the second step was carried out using the M06L (meta-GGA functional) theory with a 6-31G(d) basis set . The reliability of choosing the 6-31G(d) basis set is confirmed by investigating the convergence of basis sets for selected structures across all five charge schemes (Def2SV, LANL2DZ, 6-31G(d), 6-31G(d)+, 6-31G(d,p), 6-31G(d,p)+, and 6-31G(d,p)++ were examined; see Figure S4).…”

Section: Computational Detailsmentioning

confidence: 99%

Atomic Charge Schemes Comparison for Fe Single Atom in Graphitic Carbon: Insights from Quantum Simulations and Machine Learning

Wang,

Jin,

Liu

2023

J. Phys. Chem. C

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Single-atom catalysts (SACs), where a transitionmetal atom is embedded in graphitic carbon materials, have shown great potential as effective catalysts. The metal atom plays a major role in determining the catalytic reactivity, and substrate−metal interaction can tailor the intrinsic properties of metal, for example, the atomic partial charge. However, in quantum simulations, various charge schemes are used to assign charges for molecules and materials. It remains unclear whether the atomic partial charge of the metal in SACs is correlated across different charge schemes and if they exhibit different behaviors in response to variations in metal−substrate interactions. In this study, we investigated the behavior of Bader, Mulliken, Hirshfeld, Charge Model 5 (CM5), and Density Derived Electrostatic and Chemical 6 (DDEC6) charge schemes for Fe-centered SACs using quantum simulations and machine learning models. By tuning the structural and chemical parameters in the systems, we examined 166 Fe-centered graphene flakes and compared different charge schemes on the Fe atom. We observed that the DDEC6, Mulliken, and Hirshfeld charges exhibit more noticeable correlations than Bader and CM5 charges. Our findings also indicate that the local chemical environment plays a crucial role in determining the atomic charge of Fe in SACs and that different charge schemes present varied responses to changes in metal−substrate interactions. Additionally, we utilized machine learning (ML) models to predict all five charge schemes by gathering features from geometric, atomic, and electronic properties. Our machine learning models successfully predicted the CM5 scheme, which is primarily determined by electronic properties. However, for DDEC6, Bader, Mulliken, and Hirshfeld schemes, geometric features played a significant role, resulting in lower prediction accuracy than CM5. We expect that the insights gained from this study will contribute to a better understanding of the selection of appropriate charge schemes for SACs design.

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Nitrogen-doped fullerenes for CO₂ capture: a DFT study

Abstract: The structural and electronic properties of several Nitrogen-doped fullerenes, C60–2nN2n (n = 1–12), have been studied using density functional theory (DFT) at M06L/6-311+G(d)//M06L/6-31G(d) level. The electronic features studied using molecular...

Cited by 5 publications

References 54 publications

Molecular Electrostatic Potential Topology Analysis of Noncovalent Interactions

Molecular Electrostatic Potential Topology Analysis of Noncovalent Interactions

Hydrogen bonds ofOCNHmotif in rings in drugs: A molecular electrostatic potential analysis

Atomic Charge Schemes Comparison for Fe Single Atom in Graphitic Carbon: Insights from Quantum Simulations and Machine Learning

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Nitrogen-doped fullerenes for CO2 capture: a DFT study

Abstract: The structural and electronic properties of several Nitrogen-doped fullerenes, C60–2nN2n (n = 1–12), have been studied using density functional theory (DFT) at M06L/6-311+G(d)//M06L/6-31G(d) level. The electronic features studied using molecular...

Cited by 5 publications

References 54 publications

Molecular Electrostatic Potential Topology Analysis of Noncovalent Interactions

Molecular Electrostatic Potential Topology Analysis of Noncovalent Interactions

Hydrogen bonds ofOCNHmotif in rings in drugs: A molecular electrostatic potential analysis

Atomic Charge Schemes Comparison for Fe Single Atom in Graphitic Carbon: Insights from Quantum Simulations and Machine Learning

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Nitrogen-doped fullerenes for CO₂ capture: a DFT study