Quantum chemical and quantum dynamical studies of the photocatalytic water splitting on titanium dioxide surfaces

• Applicant: Professor Dr. Thorsten Klüner
• Subject Area: Theoretical Chemistry: Molecules, Materials, Surfaces ; Physical Chemistry of Solids and Surfaces, Material Characterisation ; Theoretical Chemistry: Electronic Structure, Dynamics, Simulation
• Term: from 2012 to 2018
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 221465315

A well-designed strategy for the development of new concepts and technologies on the subject of photocatalytic water splitting by inorganic materials (artificial photosynthesis) is based on a detailed, i.e. atomistic understanding of the underlying elementary processes. The specific goal of the current research proposal consists of the effort to simulate the photocatalytic water splitting on ideal, defect containing, and nitrogen-doped surfaces of (rutile and anatase) titania-TiO2 as accurately as possible. These surfaces represent sufficiently simple model systems which allow for the study of the relevant photocatalytic processes by modern quantum chemical and quantum dynamical approaches without relying on experimental data. This ab initio approach is based on embedded cluster models of the electronic ground state and electronically excited states involved in photocatalytic water splitting of the H2O/TiO2(110)-system and pursues accurate quantum chemical methodology beyond current density functional theory (DFT), i.e. CASSCF and CASPT-2. These methods allow for the calculation of accurate, five-dimensional potential energy surfaces of the electronic ground state and electronically excited states which form the basis for exact quantum dynamical simulations within the framework of stochastic wave packet calculations paving the way for fundamental insight into the mechanism of artificial photocatalysis in direct comparison with experimental results.

• DFG Programme: Priority Programmes
• Subproject of: SPP 1613: Regeneratively Produced Fuels by Light Driven Water Splitting: Investigation of Involved Elementary Processes and Perspectives of Technologic Implementation