Simulation of molecular and electronic structure of polyhydrogenated (n,0)-tubulenes and their analogs intercalated with lithium

Molecular and electronic structure of four polyhydrogenated (n,0)-tubulenes, namely, −C₂₄H₄−] _m (1), two isomers of composition −C₂₈H₄−] _m (2 and3), and −C₃₂H₄−] _m (4) withn benzene rings in the cross section (n=6, 7, 7, and 8, respectively), was simulated atm>1 (m is the number of repeating fragemnts). It was assumed that hydrogen atoms are attached to all carbon atoms lying on the two most distant elements of the cylinders of the corresponding tubulenes. The energy band structures of macromolecules1–4 and their Li-intercalated analogs −C₂₄H₄Li−] _m (5) −C₂₈H₄Li−] _m (two isomers,6 and7), and −C₃₂H₄Li−] _m (8), containing one Li atom per repeating unit at each center, were obtained in the EHT approximation by the crystal orbital method. Geometric parameters of repeating units of structures1–8 were found after MNDO/PM3 optimization of the energies of hydrocarbon molecules C₇₂H₂₄, C₈₄H₂₆ (two geometric isomers), and C₉₆H₂₈, containing three repeating units of corresponding tubulenes1–4 each. The conductivity types of polyhydrogenated tubulenes1–4 are the same as those of their precursors, (6,0)-, (7,0)-, and (8,0)-tubulenes. Dispersion curves of systems5–8 are much the same as those of macromolecules1–4; however, electron energy spectra of5–8 possess metallic conductivity type and the positions of Fermi levels for these systems are higher than for compounds1–4. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2061–2067, November, 1999.