Ab initio calculations, structure, NBO and NCI analyses of X H⋯π interactions

Wu, Qiyang; Su, Hongsheng; Wang, Hongyan; Wang, Hui

doi:10.1016/j.cplett.2018.01.015

Cited by 17 publications

(4 citation statements)

References 48 publications

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“…is rendered by the VMD 1.9.3 program [53] . The NCI method has been employed on numerous recent studies to understand the nature of bonding in non‐covalent interaction based complexes [54,55] . NCI analysis provides isosurface of RDG and a 2D plot of reduced density gradient ( s ) versus sign( λ 2 ) ρ. G enerally, the strong interactions are characterized by sign( λ 2 ) ρ <0, weak van der Waals by sign( λ 2 ) ρ ≅0, and non‐bonded interactions like steric repulsion by sign( λ 2 ) ρ >0 [55] .…”

Section: Resultsmentioning

confidence: 99%

“…The NCI method has been employed on numerous recent studies to understand the nature of bonding in non‐covalent interaction based complexes [54,55] . NCI analysis provides isosurface of RDG and a 2D plot of reduced density gradient ( s ) versus sign( λ 2 ) ρ. G enerally, the strong interactions are characterized by sign( λ 2 ) ρ <0, weak van der Waals by sign( λ 2 ) ρ ≅0, and non‐bonded interactions like steric repulsion by sign( λ 2 ) ρ >0 [55] . As shown in Figure 5, green surface between SO 3 and pyridine ring indicates that the interaction has dispersive character which is often observed for interactions involving π‐electrons.…”

Section: Resultsmentioning

confidence: 99%

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Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

et al. 2021

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A theoretical study has been carried out on the π‐hole based chalcogen bonding interaction between SO3 and various pyridines (XC5H4N), at the MP2=full/aug‐cc‐pVTZ level, to obtain a better insight into the nature and strength of N…S bond. Our calculations predict two different types of chalcogen bonded complexes: (1) Type‐A complex is formed via lone pair‐ π‐hole (N…S) interaction, and (2) Type‐B complex is stabilized through π‐hole‐π‐electron interaction. The binding energy of the Type‐A complexes varies between −109.78 and ‐81.56 kJ/mol whereas it ranges between −28.93 and −17.82 kJ/mol for Type‐B complexes. The nature of the N…S bond and the changes in its properties on the influence of electron donating and electron withdrawing substituents have been discussed with the help of various computational tools like AIM, NCI, SAPT and NBO analysis. The binding energy of the Type‐A complexes are found to correlate with the basicity parameters such as PA and Vs,min of the substituted pyridines. The binding energies of the pyridine complexes with SF2, SO2, CS2 and OCS are also computed for finding the effect of variation of Vs,max value of the S‐atom on the binding energy. The 2nd order hyperconjugation interaction energy between LP(N) and σ*(S−O)/LP*(S) is well correlated to the binding energy as: −ΔE=0.11E(2) −20.08. The variation in the bond distances and their corresponding vibrational frequencies of both the interacting partners (XC5H4N and SO3) are discussed in detail.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

et al. 2021

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“…The scatter plots and color-mapped surfaces of other composites are shown in Figures S30–S41 of the Supporting Information. The red, green, and blue color codes according to the value of sign (λ 2 ) ρ ranging from −0.04 to 0.02 au are used to describe destabilizing steric interactions (0.02–0.04 au), van der Waals (−0.01 to 0.01 au), and stabilizing hydrogen bond (−0.01 to −0.04 au). The color-filled RDG surfaces also indicate the type of interaction according to the color codes.…”

Section: Resultsmentioning

confidence: 99%

Interaction of Graphene Quantum Dots with Oligothiophene: A Comprehensive Theoretical Study

et al. 2019

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Graphene/polythiophene composites are widely used in a variety of optoelectronic devices and applications, e.g., as electrode materials in capacitors and solar cells, but the detailed molecular-level relationship between their structural and electronic properties is not well understood. We present a density functional theory study of these composites using model systems consisting of graphene nanosheets and nanoribbons sandwiched between oligothiophenes (up to 13 monomers in length). These systems are investigated by computing optical band gaps, UV− visible spectra, densities of states, and by analyzing noncovalent interactions in terms of the reduced density gradient. Frontier molecular orbital analysis reveals a significant decrease in the optical band gap upon increasing the concentration of graphene, which can be tuned by adjusting the proportion of graphene using larger nanoribbons. This finding has implications for device design in these materials.

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“…Establishing the strengths of these interactions and their hierarchical nature is central to future work in materials design. While information on sublimation energies could give some insight into the sum of all intermolecular forces, measurements of individual intermolecular interactions are a significant challenge and best undertaken computationally. − Early approaches to understanding the hierarchy of intermolecular forces in DTDA radicals employed a simple atom–atom potential model based on a Lennard-Jones potential for dispersion, coupled with atom-based partial charges for electrostatics derived from molecular electrostatic potential surfaces . These replicated the structural features, but the total energies were potentially unreliable since the molecular electrostatic potential (MEP)-derived charges were extracted from semi-empirical methods and additional intermolecular forces, such as charge-transfer interactions, were entirely neglected.…”

Section: Introductionmentioning

confidence: 99%

Assessment of Computational Methods for Calculating Accurate Non-covalent Interaction Energies in 1,2,3,5-Dithiadiazolyl Radicals

Nikoo

Rawson

2021

Crystal Growth & Design

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The strength of non-covalent intermolecular interactions between dithiadiazolyl (DTDA) radicals XCNSSN (X = F, Cl, Br, CN) were benchmarked using a high-level post-Hartree−Fock ab initio CCSD(T) theory with a complete basis set and corrected with a counterpoise (CP) correction for basis-set superposition error (BSSE). A range of density functional theory (DFT) functionals and basis sets were then screened to identify appropriate DFT methods which would reflect the benchmark data. These identified that minimal basis sets tended to overestimate the interaction energies, whereas inclusion of additional diffuse and polarization functions led to underestimation of these energies. The application of a CP correction for BSSE generally led to inferior performances in relation to uncorrected data for DFT calculations. The relative strengths of the intermolecular interactions were implemented to rationalize the trends in packing within the series XCNSSN (X = F, Cl, Br, CN). The nature of these interactions was also probed through an Atoms in Molecules approach which reveals intermolecular bond critical points for the different types of interactions, which are all diagnostic of non-covalent interactions between DTDA radicals. These are compared with previous experimental charge-density studies on related DTDA radicals. The best-performing DFT methods were then applied to the αand β-polymorphs of the larger radical p-NCC 6 F 4 CNSSN which was too large for benchmark studies. These confirmed the small energetic differences between α and β phases with the top five best-performing methods and functionals correctly reflecting the relative phase stabilities.

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Ab initio calculations, structure, NBO and NCI analyses of X H⋯π interactions

Cited by 17 publications

References 48 publications

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

Interaction of Graphene Quantum Dots with Oligothiophene: A Comprehensive Theoretical Study

Assessment of Computational Methods for Calculating Accurate Non-covalent Interaction Energies in 1,2,3,5-Dithiadiazolyl Radicals

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Ab initio calculations, structure, NBO and NCI analyses of X H⋯π interactions

Cited by 17 publications

References 48 publications

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO3 Molecule

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO3 Molecule

Interaction of Graphene Quantum Dots with Oligothiophene: A Comprehensive Theoretical Study

Assessment of Computational Methods for Calculating Accurate Non-covalent Interaction Energies in 1,2,3,5-Dithiadiazolyl Radicals

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Product

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Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule