Quantifying Hidden Symmetry in the Tetragonal CH$_3$NH$_3$PbI$_3$ Perovskite

Abstract

The assignment of an exact space group to the tetragonal CH$_3$NH$_3$PbI$_3$ perovskite structure is experimentally challenging and controversial in the literature. Average orientation of the methylammonium ion that gives symmetry to the experimental measurement is not captured in a static density functional theory calculation, although the quasi-I4cm and quasi-I4/mcm structures are commonly used in calculations. In this work we have developed a methodology to quantify the hidden symmetry of these structures using group theory, to enable use of symmetries in understanding spectroscopy and other properties. We study the approximate symmetry of vibrational modes, including analysis of degenerate representations, as well as the dielectric, elastic, electro-optic, Born effective charge, and Raman tensors and the dynamical matrix. Comparing to each subgroup of the full tetragonal D$_{4h}$, our results show that the quasi-I4cm is best described by the expected corresponding point group C$_{4v}$, whereas the quasi-I4/mcm (despite corresponding to point group D$_{4h}$) is best described by the lower symmetry C$_{2v}$. Our methodology can be useful generally for analysis of other soft hybrid materials or any approximately symmetric material.