engleski

London dispersion interactions in [121]tetramantane dimers

London dispersion, the attractive term of the van der Waals equation, becomes increasingly important for larger molecules since its attractive effect grows with each pairwise interaction between atoms. Dispersion is responsible for the well-known higher stability of branched alkanes as compared to their linear analogues and also plays a part in self-association of, e.g., graphenes and graphanes. Hydrocarbons are ideal for exploring dispersion effects because they are non-polar systems and their energies are easily separable into covalent and van der Waals contributions. Diamondoids are nanometer-sized hydrocarbons consisting of fused adamantane cages, and we previously used them to prepare compounds with extremely long alkane C–C bonds that were stabilized by dispersion forces. In the present work we continue our exploration of attractive dispersion interactions by studying dimers of [121]tetramantane, a higher C2h symmetric diamondoid. We performed density functional theory computations employing M06-2X and B3LYP-D3(BJ) functionals with a 6-31G(d, p) basis set to evaluate the energies of dimer structures and to quantify the dispersion contribution to dimerization.

diamondoids ; London dispersion ; computations

Humboldt Research Fellowship for Postdoctoral Researchers