Structural, thermodynamic and optical properties of MgF2 studied from first-principles theory

A detailed theoretical study of structural, electronic, elastic, thermodynamic and optical properties of rutile type MgF2 has been carried out by means of first-principles Density Functional Theory (DFT) calculations using plane wave pseudo-potentials within the local density approximation and generalized-gradient approximation for the exchange and correlation functionals. The calculated ground state properties and elastic constants agree quite well with experimental values. From the calculated elastic constants we conclude that MgF2 is relatively hard when compared to other alkaline-earth fluorides and ductile in nature. The thermodynamic properties such as heat capacity, entropy, free energy, phonon density of states and Debye temperatures are calculated at various temperatures from the lattice dynamical data obtained through the quasi-harmonic Debye model. From free energy and entropy it is found that the system is thermodynamically stable up to 1200 K. The imaginary part of the calculated dielectric function ε2(ω) could reproduce the six prominent peaks which are observed in experiment. From the calculated ε(ω), other optical properties such as refractive index, reflectivity and electron energy-loss spectrum are obtained up to the photon energy range of 30 eV. -- Graphical abstract: The calculated imaginary part ε2(ω) of the complex dielectric function ε(ω) of MgF2 as a function of photon energy is shown. The calculated ε2(ω) could reproduce the major peaks observed in experiment. All the peaks observed are corresponds to interband transitions from 'p' states of Fluorine in valence band to the 's' states of Mg in conduction band. Display Omitted Research highlights: → Structural and bonding properties. → Optical properties. → Single and polycrystalline elastic properties. → Thermodynamic properties.