Predicting properties of organic optoelectronic materials: asymptotically corrected density functional study.

Archana Rajendran, Takashi Tsuchiya, So Hirata, Tzvetelin D Iordanov

Department of Materials Science and Engineering, University of Florida, Gainesville, Florida 32611, USA.

The journal of physical chemistry. A 2012 Dec 13

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A practical computational procedure has been proposed that provides key electronic parameters of a polymer (fundamental bandgap, ionization energy, electron affinity, and intrachain electron and hole mobilities) determining its suitability as a donor or acceptor in organic optoelectronic materials. Series of oligomer calculations at the Becke3-Lee-Yang-Parr level with and without a self-contained asymptotic correction using the 6-31G** basis set were performed. The bandgap, ionization energy, and electron affinities of a polymer are extrapolated from those of its oligomers obtained from the highest occupied and lowest unoccupied orbital energies in the Koopmans-like approximation. This scheme has been applied to conjugated polymers having the poly(p-phenylene), poly(thiophene), or poly(pyrrole) backbone as well as to PCBM. The observed values of the electronic parameters have been reproduced within less than 1 eV in most cases. With the predicted values of these parameters, estimates of the open-circuit voltage and drift potential have been made for 22 valid donor-acceptor combinations. Several potentially useful combinations have been identified including the poly(thiophene):PCBM. The electron and hole mobilities have been found to correlate more strongly with the conformation (planarity) than the bandgap, but otherwise do not differ significantly.

Citation

Archana Rajendran, Takashi Tsuchiya, So Hirata, Tzvetelin D Iordanov. Predicting properties of organic optoelectronic materials: asymptotically corrected density functional study. The journal of physical chemistry. A. 2012 Dec 13;116(49):12153-62