Abstract
Calculated absorption spectra are given for linear C8H18, C10H22, C16H34 and C20H42 chains, based on the assumption of a two-phonon absorption mechanism. In the present work the normal modes of vibration of different finite chains are computed directly, without recourse to the Pitzer sampling approximation and without the assumption of strict k-selection rules. The calculated spectra are found to be much more sensitive to chain length than the experimental spectra. A possible explanation of the relative insensitivity of the observed spectra is suggested in terms of a characteristic chain segment length common to all the chains. Ironically, the apparent importance of chain segmentation in the two-phonon absorption suggests that one-phonon transitions may also play a significant role in the absorption process.
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