Comparative description of binding thermodynamic parameters of perfluorinated alkanes with polyaromatic hydrocarbons. The quantum chemical approach
E.S. Kartashynska
L.M. Litvinenko Institute of Physical Organic and Coal Chemistry
DOI: 10.26456/pcascnn/2025.17.419
Original article
Abstract: The paper presents a comparative analysis of the binding thermodynamic parameters for CnH2n+2 alkanes and their perfluorinated analogues CnF2n+2 (n = 2-14) with a graphene-like surface. The model structures of the graphene surface are performed by polyaromatic hydrocarbons of the coronene series: coronene and tricircumcoronene. The calculations are done using the quantum chemical semiempirical PM6-DH2 method, and supplemented by the results of density functional theory calculations using hybrid functionals B3LYP/6-311G** and wB97X-D4/cc-pVDZ. It has been shown that the binding of perfluorinated alkanes to a graphene surface is more energetically advantageous than conventional alkanes, which is consistent with the few experimental data on the isosteric heat of adsorption of regarded compounds. Thus, the contributions of the intermolecular C–H∙∙∙π and C–F∙∙∙π interactions to the binding enthalpy are almost identical. However, in terms of the entropy factor, these interactions differ by about two times in favor of the C–F∙∙∙π interactions. As a result, the latter ones turn out to be about 60% more energetically preferable than the C–H∙∙∙π analogues according to the binding Gibbs energy criterion.
Keywords: perfluorinated alkanes, polyaromatic hydrocarbons, adsorption, thermodynamic binding parameters, C–Fꞏꞏꞏπ interactions, semiempirical methods, density functional theory
- Elena S. Kartashynska – Dr. Sc., Leading Researcher of Supramolecular Chemistry Department, L.M. Litvinenko Institute of Physical Organic and Coal Chemistry
For citation:
Kartashynska E.S. Sravnitelnoe opisanie termodinamicheskikh parametrov svyazyvaniya perftorirovannykh alkanov s poliaromaticheskimi uglevodorodami. Kvantovo-khimicheskij podkhod [Comparative description of binding thermodynamic parameters of perfluorinated alkanes with polyaromatic hydrocarbons. The quantum chemical approach], Fiziko-khimicheskie aspekty izucheniya klasterov, nanostruktur i nanomaterialov [Physical and chemical aspects of the study of clusters, nanostructures and nanomaterials], 2025, issue 17, pp. 419-432. DOI: 10.26456/pcascnn/2025.17.419. ⎘
Full article (in Russian): download PDF file
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