The temporal population profiles of F∗, CF, and CF2
in a sharp‐edged, pulsed (500 μs), fluorocarbon discharge are examined. F∗ population rises and falls with the discharge current suggesting that electron impact of the parent fluorocarbon is the primary source of emitting fluorine atoms. Ground‐state CF and CF2
, monitored by laser‐induced fluorescence, show noticeably slower formation and decay, but a simple kinetic model assuming that each arises from direct electron impact of the parent gas fits the data. It is shown that CF can be conveniently monitored by exciting the
″=0) transition with a 193 nm ArF excimer laser.