Aspuru-Guzik, AlanDelgado, Carmen RuizFerrón, Cristina CapelOsuna, Reyes MalavéHernández, VíctorNavarrete, Juan T. LópezSanchez-Carrera, Roel2012-09-242010Sánchez-Carrera, Roel S., M. Carmen Ruiz Delgado, Cristina Capel Ferrón, Reyes Malavé Osuna, Victor Hernández, Juan T. López Navarrete, and Alán Aspuru-Guzik. 2010. Optical absorption and emission properties of end-capped oligothienoacenes: a joint theoretical and experimental study. Organic Electronics 11(10): 1701-1712.1566-1199http://nrs.harvard.edu/urn-3:HUL.InstRepos:9637920The electron–vibration coupling in a family of silyl end-capped oligothienoacenes is investigated on the basis of a joint experimental and theoretical study using UV–vis absorption and emission spectroscopies and density functional theory calculations. Well-resolved vibronic progressions are found in the low-temperature absorption and emission profiles of these silyl-functionalized organic molecules. As the size of the oligomer lengthens a bathochromic shift is observed in the near-UV–vis range, indicative of the extension of the effective π-conjugation. The absorption and emission bands are practically mirror-symmetric. The combination of two normal modes with frequencies of \( \sim 1500 cm^{−1}\) and \(\sim 500 cm^{−1}\) determines the main vibronic progression in absorption and emission for all the series, although for larger oligomers (n = 6, 7, and 8) the presence of low-frequency normal modes (\(\sim100 cm^{−1}\)) is also evident. The spacing of the vibrational features is slightly larger in absorption than in emission; this agrees with the predicted shifting of the C−C stretching modes of the inner-most ring toward the high-frequency region as a result of the reversal of the single–double C−C pattern in the electronic excited-state. Our calculations indicate that the contributions of the end-capping groups to the total relaxation energy of the \(S_0 \rightarrow S_1\) and \(S_1 \rightarrow S_0\) transitions are almost negligible. This result suggest that the vibronic structure and to a large extent the spectral profiles of the silyl end-capped oligothienoacenes are mainly determined by their respective oligothienyl core.en-USoligothienoacenesoptical propertiesreorganization energyvibronic couplingtime-dependent density functional calculationsJournal Article2012-09-2410.1016/j.orgel.2010.07.001