Combined Molecular Dynamics and Embedded-Cluster Calculations in Metal Oxide Surface Chemistry

Abstract: The development and improvement of the functionality of metal oxides in heterogeneous catalysis and other surface chemical processes can greatly benefit from an atomic-level understanding of the surface chemistry. Atomistic calculations such as quantum mechanical (QM) calculations and molecular dynamics (MD) simulations can provide highly detailed information about the atomic and electronic structure, and constitute valuable complements to experimental surface science techniques.In this thesis, an embedded-cluster approach for quantum mechanical calculations has been developed to model the surface chemistry of metal oxides. In particular, CO adsorption on the MgO(001) and CeO2(110) surfaces as well as O vacancy formation at the CeO2(110) surface have been investigated. The cluster model has been thoroughly tested by comparison with electronic structure calculations for the periodic slab model.The chemical implications of distorted surface structures arising from the surface dynamics have been investigated by combining the QM embedded-cluster calculations with force-field based MD simulations. Here QM embedded-cluster calculations were performed using surface structures sampled from the MD simulations.This combined MD+QM embedded-cluster procedure was applied to the CO adsorption on MgO(001) at 50 K and the O vacancy formation on CeO2(110) at 300 K. Significant thermal variations of the CO adsorption energy and the O vacancy formation energy were observed. It was found that these variations could be estimated using the force field of the MD simulation as an interaction model. With this approach, the QM results were extrapolated to higher temperature and doped systems.