To resolve deficiencies of existing materials for heterogeneous (photo)catalysis it is essential to understand their basic working principles and properties like absorption spectra, charge carrier mobility, or reaction kinetics with chemical accuracy. For this purpose, quantum mechanics based simulations can be of great help by providing fundamental insight into the elementary processes involved. Typically, density-functional theory (DFT) based methods are used to achieve this objective even though they fail to adequately describe charge-transfer (CT) states important for (photo)electrochemical reactions. In contrast, methods based on correlated wave function (CW) approaches are better suited as they include the correct physics for CT. Unfortunately, their high computational cost and unfavorable scaling becomes prohibitive for large systems. An accuracy-retaining solution is to split the system into different subsystems, e.g. the important catalytic center to be treated with high accuracy and the remainder of the catalyst crystal, and use embedding techniques to account for the interaction between them.<br/>In this contribution, we discuss our formally exact density functional embedding theory and highlight applications in heterogeneous catalysis with an emphasis on plasmon-induced photocatalytic processes on metal nanoparticles. In this approach, the embedding potential replacing the interaction between the subsystems is determined at the DFT level and then kept fixed in a non-self-consistent way during the subsequent embedded CW calculations. An improved description of charge transfer processes, excited states, and multiconfigurational contributions is obtained for the catalytically active subsystem, thereby overcoming the deficiencies of conventional DFT. In this way, we can gain important insight into the hot-electron(or hole)-mediated processes typical for plasmonic materials.

Embedded correlated wavefunction methods for plasmon-induced photocatalysis

251st National Meeting (2016)

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