A statistical model for the cooperative thermochromic transition of polysilanes

A statistical model for the cooperative thermochromic transition of polysilanes is proposed. The basic assumption of this treatment is that the origin of the thermochromism is the conformational transition between two ordered states, i.e., all-trans and helix structures. We have calculated the partition function of a single polysilane chain by assuming that the total conformational energy of the chain can be described by a simple sum of the nearest-neighbor interaction energies and the energies of trans, gauche(+), and gauche(-) structures. A comparison of the theoretical results with the experimental intensity of absorption maxima has enabled us to estimate the free energy of stabilization of the ordered sequences. The calculation suggests that the transition-type thermochromism is observable only when the conformational stabilization energies of the ordered sequences are large.