First-principles calculations of the electronic structure, phase transition and properties of ZrSiO4 polymorphs

Journal Article · Tue May 01 00:00:00 EDT 2012 · Computational and Theoretical Chemistry, 987(1):62–70

DOI:https://doi.org/10.1016/j.comptc.2011.03.033· OSTI ID:1037945

Du, Jincheng; Devanathan, Ramaswami; Corrales, Louis R; Weber, William J

First-principles periodic density functional theory (DFT) calculations have been performed to understand the electronic structure, chemical bonding, phase transition, and physical properties of the mineral zircon (in the chemical composition of ZrSiO4) and its high pressure phase reidite. Temperature effect on phase transition and thermal–mechanical properties such as heat capacity and bulk modulus have been studied by combining the equation of states obtained from DFT calculations with the quasi-harmonic Debye model to take into account the entropy contribution to free energy. Local density approximation (LDA) and generalized gradient approximation (GGA) DFT functionals have been systematically compared in predicting the structure and property of this material. It is found that the LDA functional provides a better description of the equilibrium structure and bulk modulus, while GGA predicts a transition pressure closer to experimental values. Both functionals correctly predict the relative stability of the two phases, with GGA giving slightly larger energy differences. The calculated band structures show that both zircon and reidite have indirect bandgaps and the reidite phase has a narrower bandgap than the zircon phase. The electronic density of states and atomic charges analyses show that bonding in the high-pressure reidite phase has a stronger covalent character.

• Research Organization: Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1037945
• Report Number(s): PNNL-SA-78940; 30472; 34899; KC0201020; TRN: US201208%%95
• Journal Information: Computational and Theoretical Chemistry, 987(1):62–70, Vol. 987, Issue 1
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
APPROXIMATIONS
BONDING
CHEMICAL COMPOSITION
ELECTRONIC STRUCTURE
ENTROPY
FREE ENERGY
FUNCTIONALS
PHYSICAL PROPERTIES
SPECIFIC HEAT
STABILITY
TEMPERATURE DEPENDENCE
ZIRCON
Zircon
Reidite
Density functional theory (DFT)
Phase transition
Electronic structure
Thermo–mechanical property
Environmental Molecular Sciences Laboratory