Figure 2.

Surface scans characterizing the CO₂/Cu₅ interaction. Left-hand upper panel: relaxed surface scan (RSS) as a function of the distance between the carbon atom and the central atom of the (planar trapezoidal) Cu₅ cluster. Middle panel: RSS as a function of one C=O distance for the (planar trapezoidal) Cu₅ cluster. Bottom panel: RSS as a function of one C=O distance for the (bipyramidal) Cu₅ cluster. Right-hand panels: Gibbs energies as a function of temperature at the energy minimum (blue and red lines) and transition state (green lines) configurations as well as the asymptote for CO desorption from the Cu₅–O product species (dotted orange line). The nonperiodic cluster model has been used.