The cold-molecule field concerns the physics and the applications of molecular systems with translational temperature well below the 1 К range. The possibility of controlling all the motion as well as the internal quantum state of a sample of molecules is a long-term goal that opens the possibility for many new experiments and measurements ranging from fundamental constants to quantum chemistry and quantum computation. Although, direct laser cooling of the translational degree of freedom of molecules is still waiting for further technological or theoretical breakthroughs and ideas, many different techniques have proven to be successful in producing different types of cold as well as ultracold (i.e. T < 1 mK) molecules.
In this chapter, we will concentrate on the description of one of these techniques: the photoassociation of laser cooled atoms. We will report on the status of the art of this technique for the case of cesium atoms, describing all the main experimental findings. In particular, we will illustrate the different photoassociation schemes for molecule formation, the detection schemes through photoionization, the molecule trapping in a magnetic or dipolar trap, the vibrational cooling into a single vibrational state and finally the present prospects for rotational cooling.