The subject of this chapter is the quantum mechanical analysis of the interaction of electromagnetic radiation with atomic transitions. The analysis is based on the Schrödinger wave equation, and in the first section, the gauge-invariant form of the external electromagnetic field is introduced. The electric dipole interaction and the long-wavelength approximation for the analysis of this interaction are discussed. The perturbative analysis of both single-photon and two-photon electric dipole interactions is presented, and density matrix analysis is introduced. The interaction of radiation with the resonances of atomic hydrogen is then discussed. The analysis is performed for both coupled and uncoupled representations. In the last section of the chapter, the radiative interactions for multielectron atoms are discussed. The Wigner–Eckart theorem and selection rules for transitions between levels characterized by coupling are developed. The effect of hyperfine splitting on radiative transitions is also briefly discussed.

The chapter begins with the introduction of the two-particle Schrödinger wave equation (SWE) and the solution of this equation for the hydrogen atom. The orbital angular momentum of the electron results from the SWE solution. The Pauli spinors are introduced, and the SWE wavefunctions are modified to account for the spin of the electron. The structure of multielectron atoms is then discussed. The discussion is focused on low-Z atoms for which Russell–Saunders or LS coupling is appropriate. Alternate coupling schemes are briefly discussed. Angular momentum coupling algebra, the Clebsch–Gordan coefficients, and 3j symbols are then introduced. The Wigner–Eckart theorem is discussed, and the use of irreducible spherical tensors for evaluation of quantum mechanical matrix elements is discussed in detail.

A sample of gas, originally treated as a single quantum system, is now described in terms of its molecular constituents, starting with the case of a single radiating molecule in an equilibrium bath of perturbers. First, the isolated radiator is considered, as if the bath had been deactivated, allowing a discussion of how its internal energy and angular momentum may change when, in the presence of an electromagnetic field , a radiant transition takes place, and of how the transition amplitude may be reduced under the Wigner–Eckart theorem. Then, the interaction between radiator and bath is reinstated, but the initial correlations between the two are neglected, so that a separate average over the bath may be taken. There is then an examination of various approximations that may be of use elsewhere. These are the restrictions to collisions that are binary in nature, the possibility that a collision may be said to follow a classical trajectory, and the validity of treating it under the impact approximation, which carries a restriction to the core region of a spectral line, but offers a great simplification when collisions may be regarded as very brief, well-separated events.