Intermolecular binding of С...H−Cl in complexes of methane, ethane, and propane with a chlorine hydride molecule

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Abstract

Quantum-chemical calculations of binary complexes with the intermolecular bond С...H−Cl formed by methane, ethane, and propane molecules with a chlorine hydride molecule were carried out by the MP2/aug-cc-pVTZ method. It is shown that the bonding of hydrocarbon with an HCl molecule is possible at different mutual orientation of monomers; at that, the properties of the formed complexes are similar to the properties of molecular systems with a typical hydrogen (H-) bond. Upon complexation, elongation of the covalent bond H−Cl is observed with a frequency shift of the respective IR band of the valence vibration to the long-wave region, as well as a chemical shift on the bridging hydrogen atom characteristic of H-bonded complexes. Analysis of the nature of intermolecular bonding included decomposition of the binding energy into components, as well as NBO analysis and study of the electron density topology by the AIM method of the Bader theory. Potential curves of intermolecular interaction and electron density shift maps when the complex is formed out of monomers are were plotted.

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About the authors

A. N. Isaev

N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences

Author for correspondence.
Email: isaevaln@ioc.ac.ru
Russian Federation, Moscow, 119991

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2. Fig. 1. Molecular complexes (1–5) formed by methane, ethane, and propane molecules with a hydrogen chloride molecule by C…H–Cl bonding. Numbers indicate interatomic distances in Å.

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3. Fig. 2. Maxima (red spheres) and minima (blue spheres) of the electrostatic potential (ESP) on the van der Waals surface of CH₄, C₂H₆, and C₃H₈ molecules. The numbers indicate the value of the ESP maxima (kcal/mol); the values ​​of multiple minima vary from –2.15 kcal/mol in the methane molecule to –3.2 kcal/mol in the propane molecule.

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4. Fig. 3. Molecular graphs of electron density constructed for complexes 1, 3, and 5 formed by methane, ethane, and propane with the HCl molecule. Purple and orange spheres correspond to the critical points (3, –3) and (3, –1), respectively; the yellow color on the graph of complex 5 shows the ring critical point (3, +1), and the brown lines denote the bond paths. The numbers indicate the distance in Å from the atomic nucleus to the critical point (3, –1) of the intermolecular contact.

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5. Fig. 4. Electron density shift maps for complexes 1, 3, and 5 constructed using MP2/aug-cc-pVTZ calculations; the contour boundary runs along the 0.0005 au isoline. Purple color indicates an increase in electron density, and blue color indicates its loss during the formation of a molecular complex from monomers.

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6. Fig. 5. Potential curves of interaction of ethane and hydrogen chloride molecules during formation of complexes 2 (red broken curve) and 3 (blue broken curve). The abscissa axis shows the distance between the carbon and hydrogen atoms of the monomers forming the intermolecular bond. The ordinate axis gives the values ​​of the energy of intermolecular interaction.

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