Vibrationally resolved emission spectra of luminescent conjugated oligothiophenes from anharmonic calculations. Issue 31 (30th July 2019)

• Record Type: Journal Article
• Authors: Madsen, Diana; Christiansen, Ove; Norman, Patrick; König, Carolin
• Is Part Of: Physical chemistry chemical physics. Volume 21:Issue 31(2019)
• Page Start: 17410
• Page End: 17422
• Publication Date: 2019-07-30
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c9cp03039e
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Anharmonic emission band profiles of oligothiophenes computed in a priori chosen reduced vibrational spaces are in good agreement with experiment. Abstract : We report on accurate and efficient calculations of vibrationally resolved emission spectra for oligothiophenes from anharmonic vibrational configuration interaction wave-function calculations in reduced vibrational spaces. These reduced spaces are chosen based on the independent mode displaced harmonic oscillator model. Good agreement with experiment is obtained for all- trans oligothiophenes with two to five rings also when employing only a few active modes. Vibrational modes incorporating inter-ring carbon–carbon stretches and a ring breathing mode are found to be the main players in the vibrational progression for the emission from the first excited electronic state for all investigated oligothiophene derivatives. The presented framework is here illustrated for oligothiophenes, but we have made no underlying system-dependent assumptions and believe it to become a valuable tool for the rational design of fluorescence biomarkers.