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Ab initio calculations and crystal structure simulations for mixed layer compounds from the tetradymite series

  • Jie Yao ORCID logo EMAIL logo , Cristiana L. Ciobanu ORCID logo , Nigel J. Cook ORCID logo , Kathy Ehrig ORCID logo , Gabriel I. Dima and Gerd Steinle-Neumann
Published/Copyright: July 31, 2024
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American Mineralogist
From the journal American Mineralogist Volume 109 Issue 8

Abstract

Density functional theory (DFT) is used to obtain structural information of seven members of the tetradymite homologous series: Bi2Te3 (tellurobismuthite), BiTe (tsumoite), Bi4Te3 (pilsenite), Bi5Te3, Bi2Te, Bi7Te3 (hedleyite), and Bi8Te3. We use the formula S(Bi2kTe3)·L[Bi2(k+1)Te3] as a working model (k = 1–4) where S and L are short and long modules in the structures. The relaxed structures show an increase in the a parameter and decrease in the interlayer distance (dsub) from Bi2Te3 (2.029 Å) to Bi8Te3 (1.975 Å). DFT-derived formation energy for each phase indicates that they are all thermodynamically stable. Scanning transmission electron microscopy (STEM) simulations for each of the relaxed structures show an excellent match with atom models. Simulated electron diffractions and reflection modulation along c* are concordant with published data, where they exist, and with the theory underpinning mixed-layer compounds. Two modulation vectors, q = γ· csub∗ (γ = 1.800–1.640) and qF = γF· dsub∗ (γF = 0.200–0.091), describe the distribution of reflections and their intensity variation along dsub∗ = 1/dsub. The γF parameter reinforces the concept of Bi2kTe3 and Bi2(k+1)Te3 blocks in the double module structures, and γ relates to dsub variation. Our model describing the relationship between γ and dsub allows prediction of dsub beyond the compositional range considered in this study, showing that phases with k >5 have values dsub within the analytical range of interlayer distance in bismuth. This, in turn, allows us to constrain the tetradymite homologous series between γ values of 1.800 (Bi2Te3) and 1.588 (Bi14Te3). Phase compositions with higher Bi/Te should be considered as disordered alloys of bismuth. These results have implications for mineral systematics and classification as they underpin predictive models for all intermediate structures in the group and can be equally applied to other mixed-layer series. Our structural models will also assist in understanding variation in the thermoelectric and topological insulating properties of new compounds in the broader tetradymite group and can support experimental work targeting a refined phase diagram for the system Bi-Te.

Keywords: Tetradymite series; mixed layer compounds; crystal structure; density functional theory; STEM simulations

Acknowledgments and funding

We appreciate the constructive comments of two anonymous reviewers and editorial handling by Jianwei Wang. This work was supported by the Australian Research Council through Linkage grant LP200100156 “Critical Minerals from Complex Ores,” co-supported by BHP Olympic Dam. We acknowledge access to the Phoenix high-performance computer (HPC) at the University of Adelaide and thank Fabien Voisin and Mark Innes for the assistance with VASP installation and HPC configuration.

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Received: 2023-04-05
Accepted: 2023-10-24
Published Online: 2024-07-31
Published in Print: 2024-08-27

© 2024 by Mineralogical Society of America

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https://doi.org/10.2138/am-2023-9018
Keywords for this article
Tetradymite series; mixed layer compounds; crystal structure; density functional theory; STEM simulations

Articles in the same Issue

  1. Fingerprinting the source and complex history of ore fluids of a giant lode gold deposit using quartz textures and in-situ oxygen isotopes
  2. Cu isotope fractionation between Cu-bearing phases and hydrothermal fluids: Insights from ex situ and in situ experiments
  3. Barium mobility in a geothermal environment, Yellowstone National Park
  4. Single-crystal elasticity of humite-group minerals by Brillouin scattering
  5. Sulfur speciation in dacitic melts using X-ray absorption near-edge structure spectroscopy of the S K-edge (S-XANES): Consideration of radiation-induced changes and the implications for sulfur in natural arc systems
  6. Ab initio calculations and crystal structure simulations for mixed layer compounds from the tetradymite series
  7. A fast open data reduction workflow for the electron microprobe flank method to determine Fe3+/ΣFe contents in minerals
  8. Machine learning applied to apatite compositions for determining mineralization potential
  9. Reconstructing volatile exsolution in a porphyry ore-forming magma chamber: Perspectives from apatite inclusions
  10. Incommensurate to normal phase transition in malayaite
  11. Raman spectroscopic measurements on San Carlos olivine up to 14 GPa and 800 K: Implications for thermodynamic properties
  12. Chemical and boron isotopic composition of tourmaline from the Yixingzhai gold deposit, North China Craton: Proxies for ore fluids evolution and mineral exploration
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