Dynamics of low-coordinated surface atoms on gold nanocrystallites

The authors highlight the importance of transient configurations of atoms on the surface of nanocrystallites, and present methodologies for their investigation. A Monte Carlo method has been developed and is used to simulate the thermodynamic equilibrium of nanometer sized Au nanocrystallites, both free and supported on a MgO(100) surface. The authors find that appreciable numbers of atoms transiently occupy adatom positions on Au(111) facets, even at room temperature. This type of dynamically appearing site is usually neglected in relation to catalysis but may have a significant activity (for CO oxidation, for example). They also observe a complex solid-solid roughening transition which involves a variety of transient local atom configurations on the surface of nanocrystallites.