Picosecond Lifetimes of Hydrogen Bonds in the Halide Perovskite CH3NH3PbBr3

Abstract

The structures and properties of organic–inorganic perovskites are influenced by the hydrogen bonding between the organic cations and the inorganic octahedral networks. This study explores the dynamics of hydrogen bonds in CH₃NH₃PbBr₃ across a temperature range from 70 to 350 K, using molecular dynamics simulations with machine-learning force fields. The results indicate that the lifetime of hydrogen bonds decreases with increasing temperature from 7.6 ps (70 K) to 0.16 ps (350 K), exhibiting Arrhenius-type behavior. The geometric conditions for hydrogen bonding, which include bond lengths and angles, maintain consistency across the full temperature range. The relevance of hydrogen bonds for the vibrational states of the material is also evidenced through a detailed analysis of the vibrational power spectra, demonstrating their significant effect on the physical properties for this class of perovskites.