The coulombic σ-hole model describes bonding in CX3I⋯Y− complexes completely

2018 ◽  
Vol 20 (35) ◽  
pp. 22849-22855 ◽  
Author(s):  
Timothy Clark ◽  
Andreas Heßelmann
Keyword(s):  
Interaction Energies ◽  
Halide Anions ◽  
Hole Model ◽  
Hole Interaction

Contrary to recent reports, the σ-hole interaction energies of complexes between the carbon tetrahalides CX3I (X = F, Cl, Br, I) and halide anions Y− (Y = F, Cl, Br, I) are described very well by the simple Coulombic σ-hole concept if it is applied properly.

scholarly journals Interaction and Polarization Energy Relationships in σ-Hole and π-Hole Bonding

Crystals ◽  
2020 ◽  
Vol 10 (2) ◽  
pp. 76 ◽  
Author(s):  
Jane S. Murray ◽  
Peter Politzer
Keyword(s):  
Electric Fields ◽  
Electrostatic Potentials ◽  
Interaction Energies ◽  
Polarization Energy ◽  
Wide Range ◽  
Energy Relationships ◽  
Hole Interaction

We demonstrate that a wide range of σ- and π-hole interaction energies can be related to (a) the electrostatic potentials and electric fields of the σ- and π-hole molecules at the approximate positions of the negative sites and (b) the electrostatic potentials and polarizabilities of the latter. This is consistent with the Coulombic nature of these interactions, which should be understood to include both electrostatics and polarization. The energies associated with polarization were estimated and were shown to overall be greater for the stronger interactions; no new factors need be introduced to account for these. All of the interactions can be treated in the same manner.

Comparison of the selectivity of [M(12-Crown-4)]+ (M=Li+, Na+, K+) complexes for halide anions and some neutral molecules; a computational study

2015 ◽  
Vol 14 (08) ◽  
pp. 1550057 ◽  
Author(s):  
Faranak Dastineh ◽  
Sadegh Salehzadeh ◽  
Mehdi Bayat ◽  
Yazdan Maghsoud
Keyword(s):  
Interaction Energy ◽  
Gas Phase ◽  
High Selectivity ◽  
Theoretical Study ◽  
Computational Study ◽  
Decomposition Analysis ◽  
Interaction Energies ◽  
Halide Anions ◽  
Bonding Interaction ◽  
M 12

A theoretical study on the selectivity of a series of [M(12C4)][Formula: see text] (M = Li[Formula: see text], Na[Formula: see text], K[Formula: see text], 12C4 = 12-crown-4) complexes for F[Formula: see text], Cl[Formula: see text] and Br[Formula: see text] anions and a number of neutral molecules (CH3CN, CH3OH, NH3, H2O, py, and 12C4) is reported. At first, it was shown that in the gas phase among all studied halide anions and neutral molecules, halides have much more bonding interaction with all [M(12C4)][Formula: see text] cations. Calculated interaction energies of above anions and [M(12C4)][Formula: see text] cations decrease from F[Formula: see text] to Br[Formula: see text]. Also the interaction energy of halide anions with [M(12C4)][Formula: see text] complexes, decreases from [Li(12C4)][Formula: see text] to [K(12C4)][Formula: see text]. The electron decomposition analysis showed that the bond between [M(12C4)][Formula: see text] complexes and both the neutral and anion guests is mainly electrostatic in nature. Then the selectivity of [M(12C4)][Formula: see text] complexes for studied anions and neutral molecules are compared in methanol, acetone, acetonitrile, and nitromethane solutions. It was shown that both the desolvation process of reactants and the strength of host–guest interactions have significant effect on the selectivities. Thus the selectivity of [Li(12C4)][Formula: see text] cation for NH3and H2O neutral molecules in solution, in contrast to the gas phase, is higher than that for bromide anion. The results of calculations showed that all [M(12C4)][Formula: see text] complexes, specially [Li(12C4)][Formula: see text], have high selectivity for F[Formula: see text] over other halide anions and neutral molecules.

scholarly journals Tetrel Bonds between Phenyltrifluorosilane and Dimethyl Sulfoxide: Influence of Basis Sets, Substitution and Competition

Molecules ◽  
2021 ◽  
Vol 26 (23) ◽  
pp. 7231
Author(s):  
Xiulin An ◽  
Xin Yang ◽  
Qingzhong Li
Keyword(s):  
Lone Pair ◽  
Basis Sets ◽  
Interaction Energies ◽  
Orbital Interactions ◽  
Topological Parameters ◽  
Tetrel Bond ◽  
Electron Withdrawing Group ◽  
Derivatives Of ◽  
Tetrel Bonds ◽  
Hole Interaction

Ab initio calculations have been performed for the complexes of DMSO and phenyltrifluorosilane (PTS) and its derivatives with a substituent of NH3, OCH3, CH3, OH, F, CHO, CN, NO2, and SO3H. It is necessary to use sufficiently flexible basis sets, such as aug’-cc-pVTZ, to get reliable results for the Si···O tetrel bonds. The tetrel bond in these complexes has been characterized in views of geometries, interaction energies, orbital interactions and topological parameters. The electron-donating group in PTS weakens this interaction and the electron-withdrawing group prominently strengthens it to the point where it exceeds that of the majority of hydrogen bonds. The largest interaction energy occurs in the p-HO3S-PhSiF3···DMSO complex, amounting to −122 kJ/mol. The strong Si···O tetrel bond depends to a large extent on the charge transfer from the O lone pair into the empty p orbital of Si, although it has a dominant electrostatic character. For the PTS derivatives of NH2, OH, CHO and NO2, the hydrogen bonded complex is favorable to the tetrel bonded complex for the NH2 and OH derivatives, while the σ-hole interaction prefers the π-hole interaction for the CHO and NO2 derivatives.

Intrinsic Stacking Interactions of Natural and Artificial Nucleobases

2019 ◽  
Author(s):  
Drew P. Harding ◽  
Laura J. Kingsley ◽  
Glen Spraggon ◽  
Steven Wheeler
Keyword(s):  
Gas Phase ◽  
Electrostatic Interactions ◽  
Density Functional ◽  
Molecular Descriptors ◽  
Stacking Interactions ◽  
Interaction Energies ◽  
Functional Theory ◽  
Binding Partner ◽  
Heavy Atoms ◽  
Wide Range

The intrinsic (gas-phase) stacking energies of natural and artificial nucleobases were explored using density functional theory (DFT) and correlated ab initio methods. Ranking the stacking strength of natural nucleobase dimers revealed a preference in binding partner similar to that seen from experiments, namely G > C > A > T > U. Decomposition of these interaction energies using symmetry-adapted perturbation theory (SAPT) showed that these dispersion dominated interactions are modulated by electrostatics. Artificial nucleobases showed a similar stacking preference for natural nucleobases and were also modulated by electrostatic interactions. A robust predictive multivariate model was developed that quantitively predicts the maximum stacking interaction between natural and a wide range of artificial nucleobases using molecular descriptors based on computed electrostatic potentials (ESPs) and the number of heavy atoms. This model should find utility in designing artificial nucleobase analogs that exhibit stacking interactions comparable to those of natural nucleobases. Further analysis of the descriptors in this model unveil the origin of superior stacking abilities of certain nucleobases, including cytosine and guanine.

On the Nature of Halide-Water Interactions: Insights from Many-Body Representations and Density Functional Theory

2019 ◽  
Author(s):  
Brandon B. Bizzarro ◽  
Colin K. Egan ◽  
Francesco Paesani
Keyword(s):  
Density Functional Theory ◽  
Charge Transfer ◽  
Molecular Orbital ◽  
Density Functional ◽  
Decomposition Analysis ◽  
Orbital Energy ◽  
Energy Decomposition Analysis ◽  
Interaction Energies ◽  
Many Body ◽  
Functional Theory

<div> <div> <div> <p>Interaction energies of halide-water dimers, X<sup>-</sup>(H<sub>2</sub>O), and trimers, X<sup>-</sup>(H<sub>2</sub>O)<sub>2</sub>, with X = F, Cl, Br, and I, are investigated using various many-body models and exchange-correlation functionals selected across the hierarchy of density functional theory (DFT) approximations. Analysis of the results obtained with the many-body models demonstrates the need to capture important short-range interactions in the regime of large inter-molecular orbital overlap, such as charge transfer and charge penetration. Failure to reproduce these effects can lead to large deviations relative to reference data calculated at the coupled cluster level of theory. Decompositions of interaction energies carried out with the absolutely localized molecular orbital energy decomposition analysis (ALMO-EDA) method demonstrate that permanent and inductive electrostatic energies are accurately reproduced by all classes of XC functionals (from generalized gradient corrected (GGA) to hybrid and range-separated functionals), while significant variance is found for charge transfer energies predicted by different XC functionals. Since GGA and hybrid XC functionals predict the most and least attractive charge transfer energies, respectively, the large variance is likely due to the delocalization error. In this scenario, the hybrid XC functionals are then expected to provide the most accurate charge transfer energies. The sum of Pauli repulsion and dispersion energies are the most varied among the XC functionals, but it is found that a correspondence between the interaction energy and the ALMO EDA total frozen energy may be used to determine accurate estimates for these contributions. </p> </div> </div> </div>

Ion solvation by dipolar aprotic solvents. An ab initio study

1987 ◽  
Vol 52 (1) ◽  
pp. 6-13 ◽  
Author(s):  
Petr Kyselka ◽  
Zdeněk Havlas ◽  
Ivo Sláma
Keyword(s):  
Ab Initio ◽  
Geometry Optimization ◽  
Molecular Structures ◽  
Dimethyl Sulphoxide ◽  
Ion Solvation ◽  
Interaction Energies ◽  
Ab Initio Study ◽  
Solvation Energies ◽  
Dipolar Aprotic Solvents ◽  
Complete Geometry Optimization

The paper deals with the solvation of Li+, Be2+, Na+, Mg2+, and Al3+ ions in dimethyl sulphoxide, dimethylformamide, acetonitrile, and water. The ab initio quantum chemical method was used to calculate the solvation energies, molecular structures, and charge distributions for the complexes water···ion, acetonitrile···ion, dimethyl sulphoxide···ion, and dimethylformamide···ion. The interaction energies were corrected for the superposition error. Complete geometry optimization was performed for the complex water···ion. Some generalizations are made on the basis of the results obtained.

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