(81f) Quantum Dynamical Modeling of CO2 Reduction Using Heterogenous Photocatalysis

Quantum dynamical methods may be employed to determine rates of reaction and efficiencies in heterogenous (photo)catalytic systems. Such simulations are also capable of giving state-specific product information, which can be coupled and compared with experimental results.  Potential energy surfaces were developed for CO₂ and its anion in the gas phase as well as adsorbed to ZnO and TiO₂ surfaces. These potential energy surfaces were identified according to the electronic state of the system. Quantum dynamical photodissociation simulations, following the time-dependent wavepacket approach, were then performed on CO₂ and its anionic counterpart to determine potential pathways towards CO₂ reduction to form CO and O. Photodissociation products and rates may thus be determined as a function of initial rovibrational states, electronic states, and wavelength of incident light.  Ultimately, these dynamical studies assist us in finding photodissocation pathways that accurately account for the photocatalytic environment, so that we may guide experimental efforts to properly tailor catalyst design and reactor conditions to achieve efficient CO₂ reduction to form chemicals and fuels.