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Using temporally and spatially resolved laser spectroscopy, we have determined the identities, approximate concentrations, effects on the local field, and kinetics of formation and loss of negative ions in RF discharges. Cl- and BCl3- are the dominant negative ions found in low-frequency discharges through Cl2 and BCl3, respectively. The electron affinity for Cl is measured to be 3.6118 Â± 0.0005 eV. Negative ion kinetics are strongly affected by application of the RF field. Formation of negative ions by attachment of slow electrons in RF discharges is governed by the extent and duration of electron energy relaxation. Similarly, destruction of negative ions by collisional detachment and field extraction is dependent upon ion energy modulation. Thus, at low frequency, the anion density peaks at the beginning of the anodic and cathodic half-cycles after electrons have attached but before detachment and extraction have had time to occur. At higher frequencies, electrons have insufficient time to attach before they are reheated and the instantaneous anion density in the sheath is greatly reduced. When the negative ion density is comparable to the positive ion density, the plasma potential is observed to lie below the anode potential, double layers form between sheath and plasma, and anions and electrons are accelerated by large sheath fields to electrode surfaces.