Abstract This chapter treats fully quantum mechanically the interaction of charged particles with a fluctuating electromagnetic field using time-dependent perturbation theory. It discusses absorption, spontaneous emission, and stimulated emission in atomic physics.
In this chapter, we discuss a purely quantum approach to the interaction between an atom and the electromagnetic field. In this treatment, the atom and electromagnetic field form a single quantum system, whose evolution is handled globally within a unified formalism. This will thus have the merit of being fully consistent from the theoretical standpoint. But the main advantage in an entirely quantum approach is that it can treat the full range of matter–radiation interaction phenomena. In particular, it provides a rigorous description of the spontaneous emission of light by an excited atom , something that falls outside the scope of the semi-classical framework applied in Chapters 2 and 3, where the lifetime of an excited atomic state had to be fed in phenomenologically. It can describe other phenomena of the same type, such as parametric fluorescence by a nonlinear crystal subjected to pumping radiation (see Chapter 7), which underlies many recent developments in quantum optics. The fully quantum approach also has the merit of allowing a simple interpretation in terms of photons for the various matter–radiation interaction processes, such as absorption, stimulated emission, scattering, and also the basic processes of nonlinear optics. Indeed, it provides a unified framework for both stimulated and spontaneous processes. Finally, it can be used to tackle completely new situations where matter and radiation interact, which lie outside the scope of any semi-classical description, such as cavity quantum electrodynamics or the production of single-photon or entangled-photons states .
Many processes, including absorption and stimulated emission occurring in lasers, can be handled using a semi-classical model for the atom–radiation interaction, in which the matter is given a quantum description, but the radiation is represented as a classical electromagnetic field (see Chapter 2). There are other phenomena that cannot be adequately described without quantizing the radiation. For example, it has been known since the 1930s that spontaneous emission can only be treated correctly using a fully quantum framework for the interaction, in which both the matter and the radiation are quantized, as we shall see in Chapter 6. However, it was not until the 1970s that situations were found in which a free electromagnetic field , far from sources, exhibited properties and behaviour that could not be described by a classical field, but which could be perfectly well interpreted in terms of a quantized field. This chapter is devoted to the quantization of the free electromagnetic field, far from the charges and currents sourcing it. This free electromagnetic field will be called radiation , and in Chapter 6 we shall specify exactly what is meant by radiation when sources are present. The canonical quantization procedure used here starts from a description of the classical dynamics of the field in the framework of the Hamiltonian formalism, the basic features of which are discussed in Section 4.1.
The basic phenomena of interaction between atoms and e.m. fields can be discussed in some detail without the need of a detailed model of the atom. Absorption and stimulated emission of radiation can be explained satisfactorily by the theory, where a classical electromagnetic wave provides a time-dependent perturbation to the energy of the atomic electrons. Laser radiation appears to a very good approximation to be a classical travelling wave of well-defined amplitude and phase. The radiation produced by a continuous laser is a good approximation to a coherent state. For conventional sources of radiation, the interaction energy is small compared with the energy an electron possesses by virtue of the attraction to the atomic nucleus, so perturbation theory produces quite acceptable results. The quantum mechanical analogy to the distortion of the classical charge cloud is given by the writing down of a general state function for the system, Ψ.
This chapter reviews the classical description of radiation. It describes how classical electromagnetic radiation interacts with a quantum mechanical particle. The general rule is that, even though the wave functions and the electromagnetic potentials change with the gauge, all physically observable quantities are independent of the gauge. The chapter also describes the process of the absorption of light by a system in terms of the effect of an external classical electromagnetic field on the system. The total emission rate is the sum of the induced and the spontaneous rates. Spontaneous emission is just the quantum mechanical version of the classical phenomenon of radiation from an accelerating charge. A very important consequence of the fact that the electromagnetic field is quantized is that there are vacuum fluctuations of the field, analogous to the zero point motion of a harmonic oscillator. Einstein gave a simple statistical argument to determine the rate at which spontaneous emission takes place.
How to deal with time-dependent potentials, what kinds of physical problems having time-dependent potentials can be solved exactly and which are to be solved with the use of perturbation theory, what are different possible forms of time-dependent perturbating fields, and semi-classical treatment of the interaction of fields with matter are the subject matters of this chapter. First order perturbation theory, computation of transition probability, transition rates and Fermi's Golden Rule for harmonic and constant perturbations, absorption, stimulated emission and dipole approximation when electromagnetic fields interact with matter, spontaneous emission and Einstein coefficients, and dipole selection rules are other topics which are dealt with in detail in the chapter. Discussions with properly justified mathematical treatment on time-dependent potentials and on the exactly solvable time-dependent two-state systems are the special foci of this chapter.
Radiation can change the energy state of matter via three optical processes: spontaneous emission, absorption and stimulated emission. In spontaneous emission, an excited atomic or molecular state decays to a lower energy state with the emission of a photon of energy equal to the difference in the quantum state energies. Photon absorption is the reverse process, with a photon causing excitation from a lower to an excited quantum state. Stimulated emission was first proposed by Einstein in a paper published in 1917. He attempted to balance spontaneous emission and photon absorption, but could not get the correct balance without the postulated process of stimulated emission (see Section 4.2). With stimulated emission, an excited quantum state is stimulated to decay to a lower quantum state by an impinging photon. The existing photon survives with another identical photon being created (so that energy is conserved). The rates at which radiative transitions occur can be calculated using quantum mechanics. The time-dependent Schrodinger equation is used with the system wavefunction comprising time-varying linear combinations of the two wavefunctions for the lower and upper quantum states. In semi-classical treatments, an atom is treated quantum mechanically with the radiation field treated classically. There is a perturbation in energy associated with, say, the electric field of the radiation interacting with the electric dipole of the atom, though other interactions can be significant if the electric dipole interaction energy is small. In absorption, for example, a differential equation representing the change in ‘weighting’ of the wavefunction from the lower to upper state is obtained. A ‘time constant’ for the speed of change represents the rate of the radiative process. We examine the quantum mechanical nature of radiation absorption in Section 10.1 before discussing (Section 10.3) another important parameter arising with radiative transitions between discrete bound quantum states: the lineshape function. Quantum Theory of the Atom–Radiation Interaction An expression for the Einstein B-coefficient for photo-absorption is derived using quantum mechanics in this section. Einstein determined the detailed balance relationship between the rates of spontaneous emission, photo-absorption and stimulated emission when light interacts with an atom by considering an atomic system of two energy levels which are in equilibrium with a black-body radiation field. We use a semi-classical treatment where the atom is treated quantum mechanically and the radiation field is treated as a classical oscillating electric field.