First-principles kinetic modeling for solar hydrogen production
Physical Chemistry of Molecules, Liquids and Interfaces, Biophysical Chemistry
Theoretical Chemistry: Molecules, Materials, Surfaces
Final Report Abstract
The work in the present project has established an important basis for a reliable modeling of solvation effects in (photo-)electrocatalytic reactions. The implemented SMPB model establishes a versatile approach to also consider ionic effects. The function-space based solution strategy optimally exploits the existing infrastructure of full-potential localized basis set DFT codes and leads to an unparalleled efficiency and stability. While ultimately only mixed explicitimplicit solvation setups will provide final (quantitative) answers, the establishment of a general parametrization protocol for the SMPB model represents an important first step. Very much in the spirit of first-principles work, the protocol leads to transferable parameters that yield a physically sound description rather than a multi-parameter fit to mathematically optimize the description of an individual system. From growing experience with other solvation models in popular DFT codes, we see this as a most valuable asset. In fact, such parameters are a prerequisite for only just emerging studies that systematically address ionic effects on surface electrocatalytic reactions. The implicit solvation functionality established in the current project represents an important pillar in the longer-term research strategy of our group. Ongoing work extends the implemented SMPB infrastructure to periodic boundary conditions to allow for efficient calculations in supercell geometries. This approach is deemed appropriate for electron-rich metal surfaces, where proton-coupled electron transfer steps are likely prevailing. The central challenge in this extension is thereby the implementation of the Ewald summation which enables a fast convergence of electrostatic potential and energy. In parallel, we aim to also couple the SMPB scheme to the QM/MM infrastructure in order to arrive at an efficient framework for the modeling of photo-electrocatalytic reactions at complex semiconductor surfaces beyond proton-coupled electron transfer, i.e. involving charged surface intermediates. Finally, we are almost finished with extending the developed SMPB parametrization protocol also to non-aqueous solvents.
Publications
- Function-Space Based Solution Scheme for the Size-Modified Poisson-Boltzmann Equation in Full-Potential DFT, J. Chem. Theory. Comput. 2016, 12, 4052
S. Ringe, H. Oberhofer, C. Hille, S. Matera, K. Reuter
(See online at https://doi.org/10.1021/acs.jctc.6b00435) - Transferable Ionic Parameters for First-Principles Poisson-Boltzmann Solvation Calculations: Neutral Solutes in Aqueous Monovalent Salt Solutions, J. Chem. Phys. 2017, 146, 134103
S. Ringe, H. Oberhofer, K. Reuter
(See online at https://doi.org/10.1063/1.4978850)
