First-principles investigation of structural, optoelectronic, mechanical, thermodynamic and hydrogen storage properties of Si-based XCsSiH₆ (X = K, Rb) hydrides

Abstract

First-principles density functional theory (DFT) calculations are employed to investigate the structural, optoelectronic, mechanical, thermodynamic, and hydrogen storage properties of XCsSiH₆ (X = K, Rb). The hydrogen atoms form discrete SiH₆ octahedra stabilized by alkali metal cations, confirming a stable cubic $F\overline 4 3m$ symmetry upon structural optimization. Both compounds exhibit both thermal and dynamical stability. The calculated gravimetric hydrogen storage capacities are 2.94wt% for KCsSiH₆ and 2.40wt% for RbCsSiH₆. Electronic band structure analysis indicates indirect band gaps of 3.14 eV (KCsSiH₆) and 3.17 eV (RbCsSiH₆), with hydrogen contributing mainly to the valence band maximum (VBM) and Cs/Rb/K atoms to the conduction band minimum (CBM). Optical property analyses of the dielectric response, absorption, and reflectivity show pronounced ultraviolet activity, suggesting suitability for optoelectronic and UV-filtering applications. Both hydrides are found to be brittle yet elastically isotropic, with KCsSiH₆ being slightly less stiff than RbCsSiH6. Comprehensive thermodynamic analysis demonstrates favorable variations in entropy, heat capacity, and Gibbs free energy up to 800 K, indicating the pronounced thermal stability of the investigated systems. Overall, XCsSiH₆ hydrides appear to be stable semiconductors with moderate hydrogen storage capacity and desirable optical properties, suitable for various energy and electronic applications.

Keywords

complex hydrides / hydrogen storage / density functional theory / mechanical stability / thermodynamic analysis

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