Efficient ab initio schemes for finding thermodynamically stable and metastable atomic structures: Benchmark of cascade genetic algorithms

Abstract

A first-principles based methodology for efficiently and accurately finding thermodynamically stable and metastable atomic structures is introduced and benchmarked. The approach is demonstrated for gas-phase metal-oxide clusters in thermodynamic equilibrium with a reactive (oxygen) atmosphere at finite pressure and temperature. It consists of two steps. At first, the potential-energy surface is scanned by means of a global-optimization technique, i.e., a massive-parallel first-principles cascade genetic algorithm for which the choice of all parameters is validated against higher-level methods. In particular, we validate a) the criteria for selection and combination of structures used for the assemblage of new candidate structures, and b) the choice of the exchange-correlation functional. The selection criteria are validated against a fully unbiased method: replica-exchange molecular dynamics. Our choice of the exchange-correlation functional, the van-der-Waals-corrected PBE0 hybrid functional, is justified by comparisons up to highest level currently achievable within density-functional theory, i.e., the renormalized second-order perturbation theory, rPT2. In the second step, the low-energy structures are analyzed by means of ab initio atomistic thermodynamics in order to determine compositions and structures that minimize the Gibbs free energy at given temperature and pressure of the reactive atmosphere.

46 pages, 12 figures

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• Oxygen vacancy mediated cubic phase stabilization at room temperature in pure nano-crystalline Zirconia films: A combined experimental and first-principles based investigation
• Determining Surface Phase Diagrams Including Anharmonic Effects
• GAtor: A First Principles Genetic Algorithm for Molecular Crystal Structure Prediction
• Theoretical evidence for unexpected O-rich phases at corners of MgO surfaces
• Theoretical insights of codoping to modulate electronic structure of TiO${}_2$ and SrTiO${}_3$ for enhanced photocatalytic efficiency
• Exploring N-rich phases in LixNy clusters for hydrogen storage at nano-scale
• Theoretical Insights into C$-$H Bond Activation of Methane by Transition Metal Clusters: The Role of Anharmonic Effects
• Structure and electronic properties of transition-metal/Mg bimetallic clusters at realistic temperatures and oxygen partial pressures
• Metastability Triggered Reactivity in Clusters at Realistic Conditions: A Case Study of N-doped (TiO${}_2$)${}_n$ for Photocatalysis