In electron-and photon-stimulated desorption (ESD/PSD), beams of energetic electrons or photons incident on a surface containing terminal bulk atoms or an adsorbed monolayer of molecules or atoms will cause electronic excitations at the surface. In the present paper we review mechanisms of ESD/PSD, as well as examples of the benefits of electron- and photon-stimulated desorption to study molecules at surfaces. Moreover, ESD ion angular distribution (ESDIAD) and angular resolved PSD (ARPSD) are also surveyed for characterizing the geometry of srufacemolecules. A schematic bonding model of adsorbed H2O molecules interacting with electronegative adsorbate (oxygen) and electropositive adsorbate (sodium) and the experimental results of ESDIAD are discussed. The ESD/PSD of polyatomic molecules are also included. The provable resulting explosion of ESD/PSD containing desorption of neutrals and negative ions is discussed.
