First Principles Estimation of Geochemically Important Transition Metal Oxide Properties

Abstract

Reactions in the mineral surface/reservoir fluid interface control many geochemical processes such as the dissolution and growth of minerals, heterogeneous oxidation/reduction, and inorganic respiration. Transition metal oxides are one of the mineral involved in these processes. This chapter describes the usage of first principles dynamical simulation methods to analyze and interpret the atom and electronic structure of these materials using plane wave density functional theory (DFT). To illustrate these types of simulations, the chapter shows variety of results for the bulk, surface, and mineral-water interface properties of the well-characterized minerals. The chapter also discusses the theoretical background of ab initio molecular dynamics (AIMD). Similar to the bulk and surface optimization calculation, DFT and DFT + U are the most common electronic structure methods used in AIMD. DFT + U is inspired by the Hubbard model, which can be used to model strongly correlated systems. Pseudopotentials are derived from first principles single-atom DFT calculations.