DFT Modeling of Polyethylene Chains Cross-linked by Selected ns¹ and ns² 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_n–M_m–PE_n 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_n–M_m–PE_n 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_n 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_m1–PE₁₅–M_m2–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.