Organic-inorganic lead halide perovskites have unusual, temperature-dependent emission characteristics.

An interatomic model potential for molecular dynamics is derived from first-principles and used to study the molecular rotations and relaxation times in methylammonium lead halide, here considered the prototypical example of a hybrid crystal with a strong reorientational dynamics. Within the limits of a simple ionic scheme, the potential is able to catch the main qualitative features of the material at zero and finite temperature and opens the way to the development of classical potentials for hybrid perovskites. In agreement with experiments and previous theoretical findings, the molecule trajectories exhibit a transition from a dynamics dominated by high symmetry directions at low temperature to a fast dynamics at room temperature in which the molecule can reorient quasi-randomly. By computing the angular time correlation function we discuss the reorientational time as a function of temperature in comparison with existing literature, providing a simple model and a clear attribution of the relaxation times in terms of their temperature dependence. This work clarifies the temperature dependence of the relaxation times and the interpretation of the experimental data in terms of the different mechanisms contributing to the molecule dynamics.

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Homologous classes of Polycyclic Aromatic Hydrocarbons (PAHs) in their crystalline state are among the most promising materials for organic opto-electronics. Following previous works on oligoacenes we present a systematic comparative study of the electronic, optical, and transport properties of oligoacenes, phenacenes, circumacenes, and oligorylenes. Using density functional theory (DFT) and timedependent DFT we computed: (i) electron affinities and first ionization energies; (ii) quasiparticle correction to the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap; (iii) molecular reorganization energies; (iv) electronic absorption spectra of neutral and ±1 charged systems. The excitonic effects are estimated by comparing the optical gap and the quasiparticle corrected HOMO-LUMO energy gap. For each molecular property computed, general trends as a function of molecular size and charge state are discussed. Overall, we find that circumacenes have the best transport properties, displaying a steeper decrease of the molecular reorganization energy at increasing sizes, while oligorylenes are much more efficient in absorbing low-energy photons in comparison to the other classes.