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Structural and electronic properties of clathrate-like hydride: MH6 and MH9 (M = Sc, Y, La)

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Abstract

Context

The addition of central metal atoms to hydrogen clathrate structures is thought to provide a certain amount of “internal chemical pressure” to offset some of the external physical pressure required for compound stability. The size and valence of the central atoms significantly affect the minimum pressure required for the stabilization of hydrogen-rich compounds and their superconducting transition temperature. In recent years, many studies have calculated the minimum stable pressure and superconducting transition temperature of compounds with H24, H29, and H32 hydrogen clathrates, with centrally occupied metal atoms. In order to investigate the stability and physical properties of compounds with H cages in which the central atoms change in the same third group B, herein, based on first-principles calculations, we systematically investigated the lattice parameters, crystal volume, band structures, density of states, Mulliken analysis, charge density, charge density difference, and electronic localization function in \(Im\overline{3}m\)-MH6 and P63/mmc-MH9 systems with different centered rare earth atoms M (M = Sc, Y, La) under a series of pressures. We find that for MH9, the pressure mainly changes the crystal lattice parameters along the c-axis, and the contributions of the different H atoms in MH9 to the Fermi level are H3 > H1 > H2. The density of states at the Fermi level of MH6 is mainly provided by H 1 s. Moreover, the size of the central atom M is particularly important for the stability of the crystal. By observing a series of properties of the structures with H24 and H29 cages wrap** the same family of central atoms under a series of pressures, our theoretical study is helpful for further understanding the formation mechanism of high-temperature superconductors and provides a reference for future research and design of high-temperature superconductors.

Methods

The first principles based on the density functional theory and density functional perturbation theory were employed to execute all calculations by using the CASTEP code in this work.

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Acknowledgements

Numerical computations were performed on Hefei advanced computing center.

Funding

This work was supported by the National Undergraduate Innovation and Entrepreneurship Training Program (grant no. 202310613084), the Fundamental Research Funds for the Central Universities (no. 2682024ZTPY054), and 2022 Experimental Teaching Research and Reform Project of Southwest Jiaotong University (20221106).

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Authors and Affiliations

  1. Bond and Band Engineering Group, School of Physical Science and Technology, Southwest Jiaotong University, Chengdu, 610031, People’s Republic of China

    Ying-** Luo, Juan Gao, Qi-Jun Liu & Dai-He Fan

  2. State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, **’an, 710072, People’s Republic of China

    Zheng-Tang Liu

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  1. Ying-** Luo
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Contributions

Ying-** Luo: data curation, investigation, writing—original draft; Juan Gao: investigation, writing—review and editing; Qi-Jun Liu: conceptualization, funding acquisition, project administration, writing—review and editing; Dai-He Fan: formal analysis; methodology; Zheng-Tang Liu: software, resources. All authors reviewed the manuscript.

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Correspondence to Juan Gao.

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Luo, YX., Gao, J., Liu, QJ. et al. Structural and electronic properties of clathrate-like hydride: MH6 and MH9 (M = Sc, Y, La). J Mol Model 30, 229 (2024). https://doi.org/10.1007/s00894-024-06034-8

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