It is demonstrated that excited van der Waals systems can relax by electron
emission via a novel interatomic mechanism. The process is analyzed by mea
ns of extensive ab initio calculations of potential energy surfaces and ele
ctronic decay rates. The electronic emission, taking place on the same time
scale as the motion of the atomic nuclei, is accompanied by interesting dy
namical effects amenable to experimental observations. These effects arise
as a consequence of the weak chemical bond in van der Waals clusters and th
e Coulomb repulsion pattern originating from electron emission.