Influence of the aggregate state on band structure and optical properties of C60 computed with different methods.

C60 and C60 based molecules are efficient acceptors and electron transport layers for planar perovskite solar cells. While properties of these <italic>molecules</italic> are well studied by <italic>ab initio</italic> methods, those of <italic>solid</italic> C60, specifically its optical absorption properties, are not. We present a combined density functional theory–Density Functional Tight Binding (DFTB) study of the effect of solid state packing on the band structure and optical absorption of C60. The valence and conduction band edge energies of solid C60 differ on the order of 0.1 eV from single molecule frontier orbital energies. We show that calculations of optical properties using linear response time dependent-DFT(B) or the imaginary part of the dielectric constant (dipole approximation) can result in unrealistically large redshifts in the presence of intermolecular interactions compared to available experimental data. We show that optical spectra computed from the frequency-dependent real polarizability can better reproduce the effect of C60 aggregation on optical absorption, specifically with a generalized gradient approximation functional, and may be more suited to study effects of molecular aggregation. [ABSTRACT FROM AUTHOR]