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 PEn-Mm-PEn 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. PEn-Mm-PEn complexes are quasiplanar with nearly parallel PE chains. Their stability is determined by covalent C-M-C bonds accompanied by noncovalent dispersion interactions between PEn 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-Mm1-PE15-Mm2-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.

Centre of Operations Computing Centre of SAS Slovak Academy of Sciences Dúbravská cesta 9 Bratislava SK 84535 Slovakia

Department of Physical and Theoretical Chemistry Faculty of Natural Sciences Comenius University in Bratislava Ilkovičova 6 Bratislava SK 84215 Slovakia

Jaroslav Heyrovský Institute of Physical Chemistry of the Czech Academy of Sciences Dolejškova 3 Prague 8 CZ 18223 Czech Republic

Slovak National Supercomputing Centre Dúbravská cesta 9 Bratislava SK 84104 Slovakia

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