(690d) Atomistic Modeling of Electrochemical and Electrocatalytic Processes

Janik, M. J. - Presenter, Pennsylvania State University

First principles, or quantum mechanical (QM) methods are widely used to investigate the energetics of adsorption and surface reactions.  These methods may be applied to investigate electrode redox processes, including ion adsorption, surface oxidation/reduction, and electrocatalytic reaction energetics.  As an example, QM methods have been used to determine key reaction energetics and recommend improved compositions of electrocatalysts for fuel cells.  In this tutorial session, the development and application of QM modeling approaches for electrochemical processes will be reviewed.  An atomistic picture of the electrode-electrolyte interface will be developed, and the challenges to applying QM approaches this interface will be discussed.  A succession of models will be detailed that build in complexities of this interface, including thermochemical approaches to representing the electron and ion chemical potentials, inclusion of electrode charging and interfacial electric fields, and representation of electrolyte distribution at the interface.  Brief discussion will be given to the use of force-field models to further represent the longer length and time scales associated with the electrochemical interface.  Numerous applications will be discussed to illustrate the application of atomistic modeling in electrochemistry, including surface oxidation and electrocatalytic reactions in fuel cells and electrolysis.  Examples systems chosen from research in our group will include borohydride oxidation, oxygen reduction and hydrogen oxidation in various electrolytes, and carbon dioxide reduction.