We report observations of inelastic collisions of atoms excited by a weak monochromatic laser field whose frequency is close to the resonance frequency of the transition from the ground state to an excited state. Our experiments use sodium atoms in a gas cell with the laser frequency detuning from resonance (||<6 GHz) much smaller than the inverse of a collision duration. In this frequency region, our results may be interpreted in terms of inelastic collisions involving virtually excited atoms. The inelastic collision rate is determined by measuring the ratio of fluorescence from the collisionally populated level to emission from the laser populated level. By studying this emission ratio as a function of perturber pressure we show that the inelastic collision rate constant for virtually excited atoms is the same as the thermally averaged rate constant for level-to-level population transfer. Measurements of the emission ratio as a function of the laser detuning from resonance explicitly show how the correlation of collision rates with excitation frequency due to the Doppler effect is lost as the laser is tuned more than several Doppler widths from line center. The collisions of virtually excited atoms fundamentally limit experiments utilizing the Doppler effect to obtain velocity-dependent excited-state collision rates. © 1984 The American Physical Society.