Ab Initio Calculation of Surface Thermochemistry for Popular Solid Transition Metal-Based Species.

This work reports the thermochemistry calculations for solid-phase periodic models of ten popular transition metal-based species. These model structures were refined to stable geometry by geometric optimization along with calculating the thermodynamic properties including enthalpy, entropy, heat capacity at constant pressure, and Gibbs free energy by DMol package via first-principles ab initio calculations. The temperature-dependent thermochemistry values were converted to a NASA seven-polynomial format. The behavior of different thermodynamic parameters based on temperature was investigated and their comparative analysis was done. A higher number of atoms tends to show higher thermodynamic values. Moreover, these thermodynamic values agree reasonably well with previously reported experimental and computational values. Metal copper shows higher thermodynamic values as compared to its oxide. The thermodynamic properties of lanthanum-based oxides have been newly calculated through the ab initio method. Amorphous structures reveal higher thermodynamic values compared to their crystalline counterparts. A comparison between different transition metal-based species gives a better understanding of the different crystalline structures and their surface sites. These calculated thermodynamic data and polynomials can be used for a variety of thermodynamic calculations and kinetic modeling.