Transition to collapsed tetragonal phase in CaFe2As2 single crystals as seen by 57Fe Mossbauer spectroscopy

TL;DR

This study uses 57Fe Mossbauer spectroscopy and ab initio calculations to analyze the structural and electronic changes in CaFe2As2 during the transition from tetragonal to collapsed tetragonal phase, revealing phonon stiffening and charge saturation effects.

Contribution

It combines experimental Mossbauer spectroscopy with density functional theory to characterize the phase transition and elucidate the stabilization mechanism of the collapsed tetragonal phase.

Findings

Phonon modes stiffen in the collapsed phase.

Quadrupole splitting is weakly temperature dependent at low T.

Charge saturation of Fe-As bonds stabilizes the collapsed phase.

Abstract

Temperature dependent measurements of 57Fe Mossbauer spectra on CaFe2As2 single crystals in the tetragonal and collapsed tetragonal phases are reported. Clear features in the temperature dependencies of the isomer shift, relative spectra area and quadrupole splitting are observed at the transition from the tetragonal to the collapsed tetragonal phase. From the temperature dependent isomer shift and spectral area data, an average stiffening of the phonon modes in the collapsed tetragonal phase is inferred. The quadrupole splitting increases by ~25% on cooling from room temperature to ~100 K in the tetragonal phase and is only weakly temperature dependent at low temperatures in the collapsed tetragonal phase, in agreement with the anisotropic thermal expansion in this material. In order to gain microscopic insight about these measurements we perform ab initio density functional theory calculations of the electric field gradient and the electron density of CaFe2As2 in both phases. By comparing the experimental data with the calculations we are able to fully characterize the crystal structure of the samples in the collapsed-tetragonal phase through determination of the As z-coordinate. Based on the obtained temperature dependent structural data we are able to propose charge saturation of the Fe - As bond region as the mechanism behind the stabilization of the collapsed-tetragonal phase at ambient pressure.