Nonresonant multiphoton ionization with time-of-flight mass spectrometry has been used to monitor the desorption of aluminum chloride (AlxCly) etch products from the Al(111) surface at 100 and 500 K during low-coverage (<5% monolayer) monoenergetic Cl-2 (0.11-0.65 eV) dosing. The desorption products in this low-coverage range show predominantly hyperthermal exit velocities under all dosing conditions. For example, with 0.27 eV incident Cl-2, the etch product was found to have a most-probable velocity of 517+/-22 m/s at an Al(111) surface temperature of 100 K. This corresponds to 22 times the expected thermal desorption translational energy for AlCl3. Cl-2 sticking probability measurements and AlxCly etch rate measurements show etching even at Cl-2 coverages of less than 5% monolayer at surface temperatures between 100 and 500 K. These experimental results are consistent with a combination of fast-time-scale surface diffusion and agglomeration of the adsorbed chlorine to form aluminum chlorides and the presence of activated AlCl3 chemisorption states having potential energies above the vacuum level. Density functional theory calculations yield results that are consistent with both our experimental findings and mechanistic descriptions. (C) 2004 American Institute of Physics.