Molecular Structures and Vibrational Spectra of trans - and cis -Polyacetylene and Their Oligoenes Revisited Using Density Functional Theory Calculations.

Polyacetylene, the most representative synthetic conducting polymer, has attracted much attention because it exhibits high conductivity upon doping. In this paper, molecular structures, electronic excitation energies, and Raman and infrared spectra were calculated using density functional theory for trans - and cis -oligoenes with various chain lengths up to the number of C═C bonds ( n ) of 100 and trans - and cis -polyacetylenes under one-dimensional periodic boundary condition. The harmonic vibrational frequencies obtained at the B3LYP/6-311G(d,p) level were scaled by the scaling factors determined with respect to the anharmonic vibrational frequencies using the B2PLYP method, in which the coefficients of the functional were optimized for trans -oligoenes. The calculated infrared and Raman frequencies reproduce reasonably well the observed frequencies for trans - and cis -polyacetylene. Based on the chain-length dependence of the calculated Raman spectra of trans -oligoenes, we proposed the possibility of longer conjugated trans -segments observed in the resonance Raman spectra of trans -polyacetylene excited at longer wavelengths of 647.1 and 1064 nm. We also elucidated the origin of the excitation-wavelength dependence of the resonance Raman spectra of trans -polyacetylene and the structure of isomerization intermediates from cis -form to trans -form. In addition, the previous assignments of Raman and infrared spectra of trans - and cis -polyacetylene were reexamined in the present study based on the chain-length dependence of the spectra.