Reaction mechanisms in heterogeneous catalysis and electrocatalysis involving cooperation between different sites from quantum mechanics

Advances in theory and methods of quantum mechanics and in supercomputers are making it practical to consider first principles (de novo) predictions of the mechanisms of complex catalytic reactions. Some recent advances in methodologies include (1) New methods of continuum solvation for electrochem. reactions (CANDLE); (2) Grand canonical QM calcns. of electrochem. catalysis at const. potential (instead of const. nos. of electrons); (3) QM Metadynamics calcns. of free energies of electrocatalysis at operational temp. and potential. We report the application of these methods to reaction mechanisms on surfaces in which two sites play a cooperative role in accelerating the reactions, including (1) Selective ammoxidn. of propane to acrylonitrile on MoVNbTeOx based catalysts; (2) The activation of CO2 and selective formation of C2 products on metal surfaces contg. overlapping oxidized and reduced regions.