@Article{cmc.2026.082702,
AUTHOR = {Elena S. Kartashynska},
TITLE = {Spontaneous 2D Film Formation of Alkanes on Isoelectronic Substrates: BN Nanosheet vs. Graphene. Quantum Chemical Semi-Empirical Approach},
JOURNAL = {Computers, Materials \& Continua},
VOLUME = {},
YEAR = {},
NUMBER = {},
PAGES = {{pages}},
URL = {http://www.techscience.com/cmc/online/detail/27829},
ISSN = {1546-2226},
ABSTRACT = {The discovery of graphene and its unique physicochemical properties has catalyzed intensive research into alternative two-dimensional (2D) materials, with a view to their prospective applications in diverse fields of physics, chemistry, and materials science. In this context, there is a notable scientific interest in developing computationally efficient theoretical approaches capable of reliably estimating key parameters of organic films deposited on 2D surfaces. This objective necessitates a rigorous selection and validation of appropriate computational methods, ensuring an optimal balance between computational cost and predictive accuracy. This study presents a method for evaluating the thermodynamic and structural characteristics of alkane monolayers on the surfaces of 2D materials: graphene and boron nitride nanosheet (BNNS). The proposed approach employs the semi-empirical PM6 method, supplemented with corrections for dispersion interactions and hydrogen bonds. This enables the calculation of large alkane aggregates interacting with surface model molecules (tricircumcoronene C<sub>150</sub>H<sub>30</sub> for graphene and B<sub>75</sub>N<sub>75</sub>H<sub>30</sub> for BNNS), allowing identification of the key interaction increments that govern monolayer formation. The calculations demonstrate that the D3H4 correction is required for an accurate description of C–H···π interactions during alkane adsorption on BNNS surfaces, whereas the DH2 correction suffices for similar interactions on graphene-like surfaces. The evaluated interaction increments reveal that C–H···π interactions are less advantageous on BNNS compared to graphene. However, unfavorable type of C–H···H–C interactions between alkane molecules counterbalance the favorable C–H···π ones, setting a threshold chain length for alkanes capable of forming crystalline films on these surfaces. According to the results, alkanes with 14 carbon atoms in the chain can spontaneously form 2D films on BNNS at standard temperature. It is one carbon atom longer than on graphene. Two packing arrangements in 2D monolayers: “straight” and “herringbone”, are analyzed. They exhibit similar clusterization Gibbs energies, with a slight disadvantage for the “herringbone” arrangement in longer-chain alkanes at standard temperature. The presence of the “herringbone” 2D structure may represent a pre-melting solid-solid phase transition, accounting for a 1.9 K difference in melting temperature, as confirmed by experimental data.},
DOI = {10.32604/cmc.2026.082702}
}