• energy landscape;
  • rational synthesis planning;
  • structure prediction

Exploring the structural diversity of a chemical system rests on three pillars. First, there is the global exploration of its energy landscape that allows one to predict which crystalline modifications can exist in a chemical system at a given temperature and pressure. Next, there is the development of new synthesis methods in solid-state chemistry, which require only very low activation energies such that even metastable modifications corresponding, for example, to minima on the landscape surrounded by low barriers can be realized. Finally, there is the theoretical design of optimal synthesis routes, again based on the study of the system's energy landscape. In this paper the energy landscape approach to the prediction of stable and metastable compounds as a function of temperature and pressure is presented, with a particular focus on possible phase transitions. Furthermore, several examples are presented, where such predicted compounds were subsequently successfully synthesized, often employing a newly developed synthesis method, low-temperature atom-beam deposition.