Reversible thermochromism in thin solid films of poly(3-hexylthiophene), or P3HT, has been studied using ultraviolet and x-ray photoelectron spectroscopies (UPS and XPS, respectively). The UPS and XPS spectra, as well as previously published optical absorption spectra, are analyzed using the results of valence effective Hamiltonian (VEH) quantum chemical calculations of the electronic structure of isolated polymer chains. The analysis of the spectra indicates that at elevated temperatures thermally induced electronic localization occurs as a consequence of thermally induced conformational disorder.

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