Superstructure reflexions in tilted perovskites part 2

TL;DR

This paper extends previous work on superstructure reflexions in tilted perovskites by including second-order terms in the structure factor expansion, providing conditions for additional reflexions with larger distortions.

Contribution

It introduces a second-order analysis of superstructure reflexions in tilted perovskites, accounting for larger distortions beyond the infinitesimal approximation.

Findings

Derived Boolean conditions for second-order superstructure reflexions.

Identified reflexions with indices of the form half-even-even-odd.

Extended the theoretical framework for analyzing perovskite distortions.

Abstract

In a previous article (Beanland & Sjokvist, 2024), we derived Boolean conditions for the appearance of superstructure reflexions in diffraction patterns from perovskites with tilted oxygen octahedra, using the structure factor equation. Assuming that the deviation from the untilted prototype perovskite structure was infinitesimally small, we expanded the structure factor as a Taylor series, truncated at the first term. This gave an elegant and simple method giving conditions on the presence or absence of superstructure reflexions. However, in real perovskite materials these distortions are sufficiently large for higher order terms to become significant, giving an additional set of superstructure reflexions. Here, we consider the second term in the expansion and show that it gives rise to second order reflexions with indices of the form half-even-even-odd. Boolean conditions for their presence are given.