Relaxation Between Bright Optical Wannier Excitons in Perovskite Solar Absorber CH$_3$NH$_3$PbI$_3$

We study the light-absorbing states of the mixed-halide perovskite CH$_{3}$NH$_{3}$PbI$_2$Cl and tri-iodide perovskite CH$_{3}$NH$_{3}$PbI$_3$ with density functional and many-body calculations to explain the desirable photovolatic features of these materials. The short-lived electron-hole bound states produced in this photovoltaic material are of halide to lead electron transfer character, with a Wannier-type exciton. Bethe-Salpeter (GW+BSE) calculations of the absorption cross section reveal strong screening of the electron-hole interaction. The atomic character of the exciton retains ligand-to-metal character within the visible spectrum, with differing degrees of localization outside the unit cell. The average electron-hole separation in the lowest exciton is found to be about 5$A^{\circ}$, slightly larger than the Pb-I bond length. Finally, we determine the role of methylammonium's dipole in the ultrafast relaxation by preparing an atomistic model of the picosecond electronic dynamics in the tri-iodide, PbI$_3$. Our model allows us to identify phonon modes which couple strongly to the electronic excitations, and explain the picosecond timescale intra-band relaxation dynamics seen in recent transient absorption experiments. We largely substantiate the conjectured three band model for the dynamics, but also identify other possible relaxation channels in the tri-iodide.

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