Mutual influence of parallel, CH/O, OH/π and lone pair/π interactions in water/benzene/water system (original) (raw)
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Nature of the water/aromatic parallel alignment interactions
Journal of Computational Chemistry, 2014
The water/aromatic parallel alignment interactions are interactions where the water molecule or one of its OAH bonds is parallel to the aromatic ring plane. The calculated energies of the interactions are significant, up to DE CCSD(T)(limit) 5 22.45 kcal mol 21 at large horizontal displacement, out of benzene ring and CH bond region. These interactions are stronger than CHÁÁÁO water/benzene interactions, but weaker than OHÁÁÁp interactions. To investigate the nature of water/aromatic parallel alignment interactions, energy decomposition methods, symmetry-adapted perturbation theory, and extended transition state-natural orbitals for chemical valence (NOCV), were used. The calculations have shown that, for the complexes at large horizontal displacements, major contribution to interaction energy comes from electrostatic interactions between monomers, and for the complexes at small horizontal displacements, dispersion interactions are dominant binding force. The NOCV-based analysis has shown that in structures with strong interaction energies charge transfer of the type p ! r*(OAH) between the monomers also exists. V
The Magnitude of the CH/π Interaction between Benzene and Some Model Hydrocarbons
Journal of The American Chemical Society, 2000
High-level ab initio calculations were carried out to evaluate the interaction between the π face of benzene and hydrocarbon molecules (methane, ethane, ethylene, and acetylene). Intermolecular interaction energies were calculated from extrapolated MP2 interaction energies at the basis set limit and CCSD(T) correction terms. The calculated benzene-methane interaction energy (-1.45 kcal/mol) is considerably smaller than that of the hydrogen bond between waters. The benzene-methane complex prefers a geometry in which the C-H bond points toward the benzene ring. The potential energy surface is very flat near the minimum, which shows that the major source of the attraction is a long-range interaction. The HF interaction energy of the complex (0.85 kcal/mol) is repulsive. The large gain of the attraction energy (-2.30 kcal/mol) by electron correlation correction indicates that dispersion interaction is the major source of the attraction. Although the electrostatic energy (-0.25 kcal/mol) is small, a highly orientation dependent electrostatic interaction determines the orientation of the C-H bond. The calculated charge distributions show that the amount of charge transfer from benzene to methane is very small. The calculated interaction energies of benzene-ethane, benzeneethylene, and benzene-acetylene complexes are -1.82, -2.06, and -2.83 kcal/mol, respectively. Dispersion interaction is again the major source of the attraction of these complexes. The electrostatic energy (-0.17 kcal/mol) is not large in the benzene-ethane complex, while the large electrostatic energies of benzeneethylene and benzene-acetylene complexes (-0.65 and -2.01 kcal/mol) show that electrostatic interaction is also important for the attraction between benzene and unsaturated hydrocarbon molecules.
Non-covalent interaction in benzene and substituted benzene: A theoretical study
Computational and Theoretical Chemistry, 2018
Non-covalent interaction is believed to play a vital role in stabilizing various complex chemical species. Herein, we have undertaken a theoretical study to understand the nature and extent of non-covalent interaction between the aromatic surfaces of benzene and its substituted derivatives with hydrogen bond donors as well as lone pair containing molecules. Molecular electrostatic potential (MESP) calculation has been used to identify the attractive zones of the aromatic surface. Symmetry adopted perturbation theory (SAPT) calculations reveal that the stability of these interactions is dominated by both electrostatic as well as dispersion interaction. Non-covalent interaction plot (NCI) analysis provided the qualitative visualization of the interaction while quantum theory of atoms in molecules (QTAIM) proved the existence of this interaction through the formation of bond and cage critical points.
Structure and electronic properties of a benzene-water solution
The Journal of Chemical Physics, 2012
Electronic properties of benzene in water were investigated by a sequential quantum mechanical/molecular dynamics approach. Emphasis was placed on the analysis of the structure, polarization effects, and ionization spectrum. By adopting a polarizable model for both benzene and water the structure of the benzene-water solution is in good agreement with data from first principles molecular dynamics. Further, strong evidence that water molecules acquire enhanced orientational order near the benzene molecule is found. Upon hydration, the quadrupole moment of benzene is not significantly changed in comparison with the gas-phase value. We are also reporting results for the dynamic polarizability of benzene in water. Our results indicate that the low energy behaviour of the dynamic polarizability of gas-phase and hydrated benzene is quite similar. Outer valence Green's function calculations for benzene in liquid water show a splitting of the gas-phase energy levels associated with the 1e 1g (π ), 2e 2g , and 2e 1u orbitals upon hydration. Lifting of the orbitals degeneracy and redshift of the outer valence bands is related to symmetry breaking of the benzene structure in solution and polarization effects from the surrounding water molecules.
Theoretical Study of Some Benzene Derivatives in Water
Revista De Chimie, 2008
Using the HyperChem programme, the influence of water on the properties of some monosubstituted aromatic compounds was studied from the point of view of the intermolecular interactions. There have been estimated some physico-chemical parameters of the benzene, fluorobenzene, chlorobenzene, bromobenzene, iodobenzene, nitrobenzene, phenol and aniline when solved in water, surrounded by one or two solvation spheres. The boundary lengths, total energies, border levels energy, dipole moments, polarizabilities, wavelengths and the probabilities of the electronic transitions have been obtained.
Physical Chemistry Research, 2022
Organic solvent or molecule directly interacts with water molecule then it shows a significant change in the stability of such solvent-water system. Polar organic solvent/molecule shows strong hydrogen bonding interaction in aqueous phase whereas nonpolar solvent shows very weak interaction. In organic solvent-water complexes, solvent plays very important role in the stability of such system, sometimes the solvent will interact with water molecule as proton donor or sometimes it will interact as proton acceptor mode. In gas phase, some common organic solvents may interact with water molecule through different ways and we try to investigate the relative stability and actual mode of interaction of such organic solvent(OS)-water complexes by using computational method. Solvent polarity also plays an important role in such organic solvent (OS)-water complexes; therefore, the effect of polarity on the interacting counterpart need to study by changing the dielectric constant of the solven...
Hydrophobic interaction and solvatochromic shift of benzene in water
Chemical Physics Letters, 1997
Monte Carlo simulations of one and two benzene molecules in water have been performed to analyze the hydrophobic hydration and hydrophobic interaction effects. Also, Monte Carlo structures have been used in the quantum mechanical calculations of the red shift of the B2u(Tr-7r *) band of benzene in water and the role of hydrophobicity analyzed. It has been found, on average, that the water molecule closest to benzene has one of the O-H bonds tangential to the benzene plane; the water-induced effect essentially doubles the benzene-benzene interaction and hydrophobicity has a small, but non-negligible, effect on the red shift of the first absorption band of benzene in water.