Understanding the initial ultrafast excited state dynamics of methylammonium lead iodide (MAPI) perovskite is of vital importance to enable its fullest utilisation in optoelectronic devices and the design of improved materials. Here we have combined advanced measurements of the ultrafast photoluminescence from MAPI films up to 0.6?eV above the relaxed excited state with cutting-edge advanced non-adiabatic quantum dynamics simulations, to provide a powerful unique insight into the earliest time behaviour in MAPI. Our joint experimental-theoretical approach highlights that the cooling of holes from deep in the valence band to the valence band edge is fast, occurring on a 100–500?fs timescale. Cooling of electrons from high in the conduction band to the conduction band edge, however, is much slower, on the order of 1–10?ps. Density of states calculations indicate that excited states with holes deep in the valence band are greatly favoured upon photoexcitation, and this matches well with the fast (100–500?fs) formation time for the relaxed excited state observed in our ultrafast PL measurements. Consequently we are able to provide a complete observation of the initial excited state evolution in this important prototypical material.
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