Phonon confinement and dispersion curves in finite polyene derivatives

We analyze the infrared and Raman spectra (both experimentally and with the aid of quantum chemical calculations) of a series of polyenals which provide us with the fortunate case of a set of polyene chains with one of the end groups consisting of a C=O group which not only does take part in the conjugation but also pulls electrons from the chain making the whole system highly polar thus affecting the vibrational transition moments. In the following we show, for the first time, that it is possible to derive experimental phonon dispersion curves and these prove to be different for each chain length. We support our experimental findings with DFT quantum chemical calculations which reproduce with sufficient accuracy the IR and Raman spectral pattern and at the same time help in disentangling the assignment of the fine structure observed in the experimental spectra.