Non-centrosymmetric, transverse structural modulation in SrAl4, and elucidation of its origin in the BaAl4 family of compounds

TL;DR

This study investigates the incommensurate transverse structural modulation in SrAl4, revealing its CDW transition, the nature of atomic displacements, and the correlation of phase transitions with interatomic distances in the BaAl4 family.

Contribution

It provides detailed structural analysis of SrAl4's CDW and incommensurate modulation, and establishes a criterion linking phase transitions to specific c/a ratios in related compounds.

Findings

SrAl4 exhibits incommensurate transverse modulation with helical atomic displacements.

The CDW transition occurs at 243 K, with a subsequent structural transition at 87 K.

A narrow c/a ratio range predicts phase transitions in XAl4-xGax compounds.

Abstract

At ambient conditions SrAl4 adopts the BaAl4 structure type with space group I4/mmm. It undergoes a charge-density-wave (CDW) transition at TCDW = 243 K, followed by a structural transition at TS = 87 K. Temperature-dependent single-crystal X-ray diffraction (SXRD) leads to the observation of incommensurate superlattice reflections at q = \sigma c* with \sigma = 0.1116 at 200 K. The CDW has orthorhombic symmetry with the acentric superspace group F222(00sigma)00s, where F222 is a subgroup of Fmmm as well as of I4/mmm. Atomic displacements mainly represent a transverse wave, with displacements that are 90 deg out of phase between the two diagonal directions of the I-centered unit cell, resulting in a helical wave. Small longitudinal displacements are provided by the second harmonic modulation. The orthorhombic phase realized in SrAl4 is similar to that found in EuAl4. Electronic structure calculations and phonon calculations by density functional theory (DFT) have failed to reveal the mechanism of CDW formation. However, DFT reveals that Al atoms dominate the density of states near the Fermi level, thus, corroborating the SXRD measurements. SrAl4 remains incommensurately modulated at the structural transition, where the symmetry lowers from orthorhombic to b-unique monoclinic. We have identified a simple criterion, that correlates the presence of a phase transition with the interatomic distances. Only those compounds XAl4-xGax(X = Ba, Eu, Sr, Ca; 0 < x <4) undergo phase transitions, for which the ratio c/a falls within the narrow range 2.51 < c/a < 2.54.