Confinement Effect on Molecular Conformation of Alkanes in Water-Filled Cavitands: A Combined Quantum/Classical Density Functional Theory Study

The depletion force exerted on an alkane molecule from surrounding solvent may greatly alter its conformation. Such a behavior is closely related to the selective molecular recognition, molecular sensors, self-assembly, and so on. Herein, we report a multiscale theoretical study on the conformational change of a single alkane molecule confined in water-filled cavitands, in which the quantum and classical density functional theories (DFTs) are combined to determine the grand potential of alkane–water system. Specifically, the intrinsic free energy of the alkane molecule is tackled by quantum DFT, while the solvent effect arising from the solvent density inhomogeneity in confined space is addressed by classical DFT. By varying the alkane chain length, pore size, and wettability of inner pore surface, we find that pore confinement and hydrophilic inner surface facilitate the alkane conformational change from extended state to helical state, which becomes more significant as the alkane chain length increases. Our findings, which are in line with previous experimental observations, provide not only the microscopic mechanism but also theoretical guidance for elaborately manipulating molecular conformation at the nanoscale.