First-Principles Insights into the Relative Stability, Physical Properties, and Chemical Properties of MoSe₂

A fascinating transition-metal dichalcogenide (TMDC) compound, MoSe₂, has attracted a lot of interest in electrochemical, photocatalytic, and optoelectronic systems. However, detailed studies on the structural stability of the various MoSe₂ polymorphs are still lacking. For the first time, the relative stability of 11 different MoSe₂ polymorphs (1H, 2H, 3H_a, 3H_b, 2T, 4T, 2R₁, 1T₁, 1T₂, 3T, and 2R₂) is proposed, and a detailed analysis of these polymorphs is carried out by employing the first-principles calculations based on density functional theory (DFT). We computed the physical properties of the polymorphs such as band structure, phonon, and elastic constants to examine the viability for real-world applications. The electronic properties of the involved polymorphs were calculated by employing the hybrid functional of Heyd, Scuseria, and Ernzerhof (HSE06). The energy band gap of the polymorphs (1H, 2H, 3H_a, 3H_b, 2T, 4T, and 2R₁) is in the range of 1.6–1.8 eV, coinciding with the experimental value for the polymorph 2H. The covalent bonding nature of MoSe₂ is analyzed from the charge density, charge transfer, and electron localization function. Among the 11 polymorphs, 1H, 2H, 2T, and 3H_b polymorphs are predicted as stable polymorphs based on the calculation of the mechanical and dynamical properties. Even though the 4T and 3H_a polymorphs’ phonons are stable, they are mechanically unstable; hence, they are considered to be under a metastable condition. Additionally, we computed the direction-dependent elastic moduli and isotropic factors for both mechanically and dynamically stable polymorphs. Stable polymorphs are analyzed spectroscopically using IR and Raman spectra. The thermal stability of the polymorphs is also studied.