The ablation plumes arising after irradiation of graphite, silicon, copper and aluminum with a pulsed nanosecond ArF (λ=193 nm) laser at fluences between 2 and 20 J cm-2 in vacuum are studied and compared. The neutral and ionic components in the ablation plume have been measured via quadrupole mass spectrometry and ion probes, respectively. Additional information about the degree of ionization and the velocities of singly and multiply charged ions in the plume have been deduced via optical emission spectrometry, and the electron velocity distributions have been measured with Langmuir probes. Probing the plasma properties with this range of techniques is shown to provide a rather detailed picture of the ablation characteristics. The velocity distributions of the neutral atoms are comparatively narrow (∼1 km s-1 full width at half maximum) and peaked at a center of mass velocity of ∼3–4 km s-1. Their general form is reminiscent of those of species expanding supersonically from a pulsed nozzle. The electron and ion velocity distributions are much broader, and centered at much higher velocities (and kinetic energies). The relative ion yield, and the overall degree of ionization, both increase with increasing fluence and scale inversely with the ionization potentials of the respective target materials. Both charged components are found to be accelerating at short distances from the target. Such effects have been rationalized by assuming that incident laser radiation ionizes (by multiphoton ionization) neutral species ablated from the target surface, and that these ions and electrons then act as “seeds” for subsequent plume heating, ionization and plasma formation by inverse bremsstrahlung. This a- bsorption due to inverse bremsstrahlung ensures the incident laser intensity is highest at the outer edge of the expanding plume. The outer region thus receives preferential excitation and heating—traditionally pictured in terms of the so-called two electron temperature model. Some of the resulting “hot” electrons escape from this coronal region, leading to an overall charge imbalance within the plasma, which manifests itself as an acceleration (driven by Coulombic interactions) of the charged components within the plume. © 2003 American Institute of Physics.