This chapter considers an atom as a quantum mechanical system. But the electromagnetic radiation will be treated as classical waves described by the Maxwell equations. The treatment is called semi-classical. Quantum mechanics describes an atom as a quantized system with a set of discrete energy levels. Each energy level is designated by a set of quantum numbers like the principal quantum of the Rydberg level and the quantum numbers representing the orbital, spin and total angular momentum. A molecule will have a different set of quantum numbers arising from its rotational and vibrational motions. Atoms in a solid have energy levels in the form of a band. The observed spectrum due to spontaneous emission from a collection of atoms is not monochromatic, but it is spread over a certain range of frequencies. The absorption spectrum also shows that the atom does not absorb at a single frequency, but it is spread over a band of frequencies around the resonance frequency.
This chapter considers an atom as a quantum mechanical system. But the electromagnetic radiation will be treated as classical waves described by the Maxwell equations. The treatment is called semi-classical. Quantum mechanics describes an atom as a quantized system with a set of discrete energy levels. Each energy level is designated by a set of quantum numbers like the principal quantum of the Rydberg level and the quantum numbers representing the orbital, spin and total angular momentum. A molecule will have a different set of quantum numbers arising from its rotational and vibrational motions. Atoms in a solid have energy levels in the form of a band. The observed spectrum due to spontaneous emission from a collection of atoms is not monochromatic, but it is spread over a certain range of frequencies. The absorption spectrum also shows that the atom does not absorb at a single frequency, but it is spread over a band of frequencies around the resonance frequency.
We investigate in this chapter the general problem of the interaction of an atom (or a molecule) and a classical electromagnetic field. Its importance derives firstly from the fact that a large part of our knowledge of atoms is obtained from a study of the radiation they absorb or emit (we shall consider equally visible radiation and radio-frequency and X-rays) and, secondly, that the interaction with matter modifies the propagation of the electromagnetic field itself, notably through absorption, refraction or scattering. The interactions of atoms with light therefore encompass a vast range of physical effects that we could not hope to cover adequately in a single chapter. In this chapter we shall therefore present the fundamental features of the interaction of an atom, which will be treated quantum mechanically, with a classical electromagnetic field, that is an electromagnetic field described by real electric and magnetic vectors obeying Maxwell's equations. A rigorous description of the atom–light interaction would have to take into account the quantum nature of light. This we shall leave to Chapter 6. It turns out, nevertheless, that many important results can be obtained from the semi-classical viewpoint adopted here (although it is perhaps more appropriate to refer to this treatment as ‘semi-quantized’).
We treat the interaction between an electromagnetic radiation bath and a material system in the semi-classical picture: the radiation is treated according to the Maxwell equations, but the process of emission/absorption is described through the concept of a photon; on the other hand, the material system is modelled according to quantum mechanics, assuming a discrete two-level energy spectrum. This very simple model allows one to elaborate the elementary theory of the absorption/emission coefficients, both for the spontaneous and for the stimulated processes which will be described within the electric dipole approximation. Selection rules for allowed transitions are eventually obtained and the nature of high-order transition is briefly outlined. Finally, a qualitative description of the light amplification by stimulated emission of radiation is presented.
In this chapter a quantum mechanical treatment of atomic response to the fields of an electromagnetic wave is presented. Absorption and emission of energy by atoms involves transition between their quantized energy levels driven by an interaction Hamiltonian. Schrodinger equation is used to derive the equations of motion for the density matrix of the atom, which is better suited to include the effects of mechanisms other than the interaction Hamiltonian – collisions, level decays, level shifts, etc. that also affect the state of the atom. Using the density matrix equation of motion and focusing on two atomic levels, induced dipole moment for a single two-level atom and polarization and susceptibility for a collection of two-level atoms, including the effects of level decays, and collisions, are calculated. Equations of motion for level populations are also derived. These expressions naturally predict stimulated emission as well as absorption. Expressed in terms of spontaneous emission rate they confirm the validity of equations derived in Chapter 5 using the dipole oscillator model of atomic response. The limit in which quantum mechanical equations for atomic response reduce to the classical dipole oscillator equations is also discussed.
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.
The absorbed/emitted radiation will be treated classically, as a monochromatic plane wave, whereas the atomic system that can absorb/emit such radiation will be described quantum-mechanically. However, no incident radiation beam is needed, and the atom “falls down” after a certain time interval to the ground state without any external reason. In the spontaneous emission processes the emitting atom can be thought of as a classical oscillating dipole, whose amplitude decreases due to the energy loss through the radiation. If an ensemble of identical atoms is considered and if, for simplicity, each atom emits radiation with the same spectral shape and full width at half maximum, it is impossible to ascribe a definite spectral component with intensity to a definite atom. In this case, such a broadening is identical for all atoms in the ensemble. On the microscopic scale, absorption of radiation is reduced to the transitions between pairs of energy levels of a discrete atomic spectrum.
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.