The semiconducting conjugated polymers, poly-phenylene-vinylene (PPV), are studied using linear and non-linear optical spectroscopy methods: ultra-fast optical spectroscopy, optical absorption, and luminescence. Study of polarization resolved absorption and excitation spectra at room temperature revealed strong anisotropy of the optical responses. Microscopic interpretation of the results is based of the first principal analysis of the electronic structure of PPV using the density functional theory (DFT). The dominant contribution of the optical excitations in visible spectral range is related to the delocalized pi-electronics of the PPV chains. Time-resolved luminescence measurements indicate the separate contributions from electronic transitions associated to the localized and delocalized electrons in PPV.
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