Non-Condon effect on charge transport in dithiophene-tetrathiafulvalene crystal

Combining first-principles calculations and non-Condon charge transfer rates proposed by us recently [Y. Zhao and W. Z. Liang, J. Chem. Phys. 130, 034111 (2009)], we investigated non-Condon effect on charge carrier mobility of organic semiconductor dithiophene-tetrathiafulvalene (DT-TTF) crystal. The first-principles results reveal that only several high-frequency intramolecular vibrational modes dominate the reorganization energy, and the nuclear-coordinate dependence of electronic coupling prefers to perform an exponential or Gaussian property for most intermolecular modes rather than a linear one as assumed in conventional models. Furthermore, the electronic coupling of an isolated DT-TTF dimer is indeed affected by the surrounding molecules. The predicted non-Condon mobilities with use of the obtained structure parameters are always greater than those from Condon approximation, and the non-Condon dynamic disorder is not important for DT-TTF, which is also confirmed by molecular dynamics simulation. More interestingly, the bandlike property can be predicted under the hopping mechanism when the nuclear tunneling is incorporated.