Low-frequency Raman spectrum of 2D layered perovskites: Local atomistic motion or superlattice modes?

We report the low-frequency Raman spectrum (ω = 10 cm−1–150 cm−1) of a wide variety of alkylammonium iodide based 2D lead halide perovskites (2D LHPs) as a function of A-site cation (MA = methylammonium and FA = formamidinium), octahedral layer thickness (n = 2–4), organic spacer chain length (butyl-, pentyl-, hexyl-), and sample temperature (T = 77 K–293 K). Using density functional theory calculations under the harmonic approximation for n = 2 BA:MAPbI, we assign several longitudinal/transverse optical phonon modes between 30 cm−1 and 100 cm−1, the eigendisplacements of which are analogous to that observed previously for octahedral twists/distortions in bulk MAPbI. Additionally, we propose an alternative assignment for low-frequency modes below this band (