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

Abstract

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 DMol3 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.

Thermodynamic properties calculations of Cu‐based species

“…11 Arshad et al conducted a first principle investigation to determine the thermodynamic properties of solid transition metal-based species. 19 The prediction model for calculating the thermodynamic equilibrium temperature of copper-based shape-memory smart materials was demonstrated by Eskİl et al 20 While these studies have contributed significantly to the understanding of thermodynamic properties in specific contexts, our research builds upon these foundations by investigating a broader spectrum of copper-based species. In particular, we explore systems with a higher number of atoms and layers, focusing on binary and complex compounds that have not been extensively studied before.…”

“…Arshad et al. conducted a first principle investigation to determine the thermodynamic properties of solid transition metal‐based species 19 . The prediction model for calculating the thermodynamic equilibrium temperature of copper‐based shape‐memory smart materials was demonstrated by Eskİl et al 20 .…”