STM experiment and atomistic modelling hand in hand: individual molecules on semiconductor surfaces

When the scanning tunnelling microscope was invented, the world was amazed at the atomic resolution images of surfaces which could be obtained. It soon became apparent that it was one thing to obtain an image, and quite another to understand the structure that was seen. Happily the developments in real space experimental techniques for studying surfaces have been accompanied by developments in real space theoretical techniques for modelling electronic structure and bonding at surfaces. The aim of this review is to describe how and why STM experiments and atomistic modelling should be combined and what they can then be expected to tell us. A summary is given of the experimental methods for theorists and vice versa, and their relationship is illustrated using a number of case studies where they have been used together. To give the review a coherent focus the examples are confined to studies of adsorbed molecules on semiconductor surfaces, in particular Si(001) and GaAs(001). Questions thus addressed include: How are experimental images and structural modelling linked by tunnelling theory? What can they tell us together that we could not learn from experiment or theory alone? What can we learn about atomic positions and bonding at semiconductor surfaces with and without adsorbed molecules? How many different ways are there to relate images to calculations?