DFT Modeling of Polyethylene Chains Cross-linked by Selected <i>n</i>s¹ and <i>n</i>s² Metal Atoms

We analyze the structures, stabilities, and thermochemical properties of polyethylene (PE) oligomer chains cross-linked by metal (M) atoms through C-M-C bonds. Representative PE_<i>n</i>-M<i>_m</i>-PE_<i>n</i> complexes contain between 7 and 15 carbon atoms in each oligomer and one to three Li, Be, Mg, Zn, Ag, or Au cross-linking metal elements. PE_<i>n</i>-M<i>_m</i>-PE_<i>n</i> complexes are quasiplanar with nearly parallel PE chains. Their stability is determined by covalent C-M-C bonds accompanied by noncovalent dispersion interactions between PE_<i>n</i> chains. Using the CAM-B3LYP+D3BJ+ABC functional, the binding energies of PE₁₅-M-PE₁₅ with respect to two PE₁₅ radicals and metal fragments are -225, -230, -322, -551, -289, and -303 kJ/mol for Li, Ag, Au, Be, Mg, and Zn atoms, respectively. Entropy contributions (109 to 121 kJ/mol at 298.15 K) destabilize all complexes significantly. With two cross-linking metal elements in PE₁₅-M₂-PE₁₅ complexes, binding energies are about double. Complexes with several open-shell Li, Ag, or Au doublet atoms have spins located on separated C-M-C bonds. High-spin PE₁₅-M_<i>m</i>1-PE₁₅-M_<i>m</i>2-PE₁₅ complexes of three PE oligomers cross-linked by up to five doublet metal atoms create parallel PE tubes, which are suggested as elementary cells for modeling magnetic polymer tubes.