On-the-fly ab initio semiclassical dynamics: identifying degrees of freedom essential for emission spectra of oligothiophenes.

Vibrationally resolved spectra provide a stringent test of the accuracy of theoretical calculations. We combine the thawed Gaussian approximation (TGA) with an on-the-fly ab initio (OTF-AI) scheme to calculate the vibrationally resolved emission spectra of oligothiophenes with up to five rings. The efficiency of the OTF-AI-TGA permits treating all vibrational degrees of freedom on an equal footing even in pentathiophene with 105 vibrational degrees of freedom, thus obviating the need for the global harmonic approximation, popular for large systems. Besides reproducing almost perfectly the experimental emission spectra, in order to provide a deeper insight into the associated physical and chemical processes, we also develop a novel systematic approach to assess the importance and coupling between individual vibrational degrees of freedom during the dynamics. This allows us to explain how the vibrational line shapes of the oligothiophenes change with increasing number of rings. Furthermore, we observe the dynamical interplay between the quinoid and aromatic characters of individual rings in the oligothiophene chain during the dynamics and confirm that the quinoid character prevails in the center of the chain.

• Publication year

  2014

• Venue

  Journal of Chemical Physics

• Publication date

  2014-06-12

• Fields of study

  Materials Science, Physics, Chemistry, Medicine

• Identifiers
  DOI 10.1063/1.4884718arXiv 1406.3222PMID 24985625
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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