AbstractWe discuss the recent first principles calculations of the properties of interfaces between metals and oxides. This type of calculation is parameter-free, and exploits the density functional theory in the local density approximation to obtain the electronic structure of the system. At the same time the equilibrium atomic structure is sought, which minimises the excess energy of the interface. Up to now calculations of this type have been made for a few model interfaces which are atomically coherent, that is with commensurate lattices. Examples are Ag/MgO and Nb/Al2O3. In these cases it has been possible to predict the structures observed by high resolution electron microscopy. The calculations are actually made in a supercell geometry, in which there are alternating nanolayers of metal and ceramic. Because of the effectiveness of metallic screening in particular, the interfaces between the nanolayers do not interfere much with each other.Besides the electronic structure of the interface, such calculations have provided values of the ideal work of adhesion. Electrostatic image forces in conjunction with the elementary ionic model provide a simple framework for understanding the results.An important role of such calculations is to develop intuition about the nature of the bonding, including the effects of charge transfer, which has formerly only been described in an empirical way. It may then be possible to build atomistic models of the metal/ceramic interaction which have a sound physical basis and can be calibrated against ab initio results. Simpler models are necessary if larger systems, including misfit dislocations and other defects, are to be simulated, with a view to understanding the atomic processes of growth and failure. Another area in which ab initio calculations can be expected to contribute is in the chemistry of impurity segregation and its effect at interfaces. Such theoretical tools are a natural partner to the experimental technique of high resolution electron energy loss spectroscopy for studying the local chemical environment at an interface.
Fermi orbital self-interaction corrected electronic structure of molecules beyond local density approximation