Performance of common density functionals for excited states of tetraphenyldibenzoperiflanthene

Abstract

Time-dependent density functional theory is the method of choice to efficiently calculate excitation spectra with the functional and basis set choice allowing to compromise between accuracy and computational cost. In this work the performance of different functionals as well as the second-order approximate coupled cluster singles and doubles model CC2 is evaluated by comparing the results to experimental results of the example molecule tetraphenyldibenzoperiflanthene (DBP). Functional choice has a significant impact on the spectrum of DBP. The performance of a number of different functionals was evaluated, quantified, and, where possible, discussed. The best functional, tuned-CAM-B3LYP, is used to investigate DBP on a surface of hexagonal boron nitride (h-BN). The resulting spectrum shows excellent agreement with experimental results for a monolayer of DBP on h-BN.