Reduction of Copper Oxide by Formic Acid: an ab-initio study

Four cluster models for a copper(I)oxide (111) surface have been designed, of which three were studied with respect to their applicability in density functional calculations in the general gradient approximation. Formic acid adsorption on these systems was modelled and yielded four different adsorption structures, of which two were found to have a high adsorption energy. The energetically most favourable adsorption structure was further investigated with respect to its decomposition and a few reactions with adsorbed H and OH species using synchronous transit methods to estimate reaction barriers and single point energy calculations for the reaction energy.:1 Introduction 1.1 Preliminary Work 1.2 Known Reactions and Issues 1.3 Overview of Reactions and Species involved in Formic Acid Decomposition 2 Theoretical Background 2.1 The Schrödinger-Equation 2.2 Density Functional Theory 2.3 Exchange-Correlation Functionals 2.4 The Self-Consistent-Field Procedure 2.5 Geometry Optimization and Transition State Searches 2.6 Kinetics 3 Computational Details 3.1 Synchronous Transit Schemes 3.2 Transition State Searches using Eigenvector Following 4 Model System 5 Results and Discussion 5.1 Geometry of the Cu2O cluster structures 5.2 Adsorption of formic acid 5.3 Decomposition and Reaction Paths 5.3.1 Vibrational Analysis of the adsorbed Formic Acid Molecule 5.3.2 Reaction Modelling using Linear Synchronous Transit 5.3.3 Transition State Searches using Eigenvector Following 6 Summary and Outloo