The review describes and interprets the basic phenomena recently observed in the interaction between free atoms and laser radiation. Some of these have been known for a long time in magnetic resonance but in the optical range, the situation is strongly modified because of spontaneous emission and the Doppler effect. Therefore, particular attention is paid to resonance fluorescence and Doppler-free spectroscopy but without dwelling on applications. Transient effects are also discussed, but all the phenomena which characterize, not specifically the interaction between atoms and fields, but the free evolution of atoms after coherent excitation are ignored. Pulse propagation experiments are described in detail and multiphoton processes are considered, with special emphasis on Doppler-free multiphoton excitation and resonant multiphoton ionization.
Fluorescence-dip spectroscopy based on an optical double resonance is used to probe the Stark splitting in highly excited Rydberg states of atomic hydrogen. After Doppler-free two-photon excitation to
n=3, fluorescence at Balmer $\ensuremath{\alpha}$ is observed. When the radiation of a second laser is tuned over the resonance between
n=3 and a Rydberg state, the Stark splitting manifests itself as a series of dips in the Balmer- $\ensuremath{\alpha}$ fluorescence intensity. Rydberg states up to
n=55 can be identified. The minimum detectable electric field is
5V/cm. This is about an order of magnitude more sensitive than other laser-induced fluorescence techniques.