Benchmark Torsional Potentials of Building Blocks for Conjugated Materials: Bifuran, Bithiophene, and Biselenophene.

Abstract

The utility of π-conjugated oligomers and polymers continues to grow, and oligofurans, oligothiophenes, and oligoselenophenes have shown great promise in the context of organic electronic materials. Vital to the performance of these materials is the maintenance of planarity along the conjugated backbone. Consequently, there has been a great deal of work modeling the torsional behavior of these prototypical components of conjugated organic materials both in the gas and condensed phases. Such simulations generally rely on classical molecular mechanics force fields or density functional theory (DFT) potentials. Unfortunately, there is a lack of benchmark quality, converged ab initio torsional potentials for bifuran, bithiophene, and biselenophene against which these lower level theoretical methods can be calibrated. To remedy this absence, we present highly accurate torsional potentials for these three molecules based on focal point analyses. These potentials will enable the benchmarking and parametrization of DFT functionals and classical molecular mechanics force fields. Here, we provide an initial assessment of the performance of common DFT functional and basis set combinations, to identify methods that provide robust descriptions of the torsional behavior of these prototypical building blocks for conjugated systems.