Ab initio atomistic thermodynamics and statistical mechanics of surface properties and functions

Abstract

Previous and present "academic" research aiming at atomic scale understanding is mainly concerned with the study of individual molecular processes possibly underlying materials science applications. Appealing properties of an individual process are then frequently discussed in terms of their direct importance for the envisioned material function, or reciprocally, the function of materials is somehow believed to be understandable by essentially one prominent elementary process only. What is often overlooked in this approach is that in macroscopic systems of technological relevance typically a large number of distinct atomic scale processes take place. Which of them are decisive for observable system properties and functions is then not only determined by the detailed individual properties of each process alone, but in many, if not most cases also the interplay of all processes, i.e. how they act together, plays a crucial role. For a "predictive materials science modeling with microscopic understanding", a description that treats the statistical interplay of a large number of microscopically well-described elementary processes must therefore be applied. Modern electronic structure theory methods such as DFT have become a standard tool for the accurate description of individual molecular processes. Here, we discuss the present status of emerging methodologies which attempt to achieve a (hopefully seamless) match of DFT with concepts from statistical mechanics or thermodynamics, in order to also address the interplay of the various molecular processes. The new quality of, and the novel insights that can be gained by, such techniques is illustrated by how they allow the description of crystal surfaces in contact with realistic gas-phase environments.

24 pages including 17 figures, related publications can be found at http://www.fhi-berlin.mpg.de/th/paper.html

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• The steady-state of heterogeneous catalysis, studied by first-principles statistical mechanics
• Kinetic hindrance during the initial oxidation of Pd(100) at ambient pressures
• The Pd(100)-(SQRT(5) x SQRT(5) R27^o)-O surface oxide revisited
• Why is a noble metal catalytically active? The role of the O-Ag interaction in the function of silver as an oxidation catalyst
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Cited by in corpus (19)

• First-principles kinetic Monte Carlo simulations for heterogeneous catalysis, applied to the CO oxidation at RuO2(110)
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• Single-Atom Alloy Catalysts Designed by First-Principles Calculations and Artificial Intelligence
• Alloy surface segregation in reactive environments: A first-principles atomistic thermodynamics study of Ag3Pd(111) in oxygen atmospheres
• CO oxidation on Pd(100) at technologically relevant pressure conditions: A first-principles kinetic Monte Carlo study
• On the accuracy of first-principles lateral interactions: Oxygen at Pd(100)
• Efficient ab initio schemes for finding thermodynamically stable and metastable atomic structures: Benchmark of cascade genetic algorithms
• Conversion of La${}_2$Ti${}_2$O${}_7$ to LaTiO${}_2$N via Ammonolysis: An ab-initio Investigation
• First-principles statistical mechanics approach to step decoration at surfaces
• Exploring N-rich phases in LixNy clusters for hydrogen storage at nano-scale
• A Hybrid-DFT Study of Intrinsic Point Defects in $M{X}_2$ ($M$=Mo, W; $X$=S, Se) Monolayers
• Surface reconstruction of tetragonal methylammonium lead triiodide
• Structure and electronic properties of transition-metal/Mg bimetallic clusters at realistic temperatures and oxygen partial pressures
• First-principles lattice-gas Hamiltonian revisited: O-Pd(100)
• Modelling the size of Nitrogen c(2x2) islands on Cu(001) with elastic multisite interactions
• Adatom pair distribution up to half coverage: O-Pd(100)
• Metastability Triggered Reactivity in Clusters at Realistic Conditions: A Case Study of N-doped (TiO${}_2$)${}_n$ for Photocatalysis
• Understanding oxide surface stability: Theoretical insights from silver chromate
• Adatom generated spatially oscillating strain fields on isotropic and other substrates