Recent advances in both first principles computational methodologies for co
mplex systems and qualitative understanding of the electronic structure of
solids now make a real dialogue between theoreticians and experimentalists
possible. We discuss how this situation can lead to a fruitful interplay in
inorganic solid state chemistry, considering selected examples, such as th
e structure of gold nanoclusters and nanowires, the absorption of atoms and
molecules and growth of thin films on silicon surfaces, understanding the
development of some structural modulations in low-dimensional transition me
tal oxides and bronzes, and the control of the transport properties of hybr
id organic-inorganic charge transfer molecular solids.