In many practical cases a stationary system is perturbed in some way, inducing it to undergo transitions between the otherwise stationary states. Perhaps the best example concerns the radiative transitions of atomic electrons in which the disturbance of an external electromagnetic field causes the electrons to jump between energy levels, emitting or absorbing photons. Equation is a statement of the classical law of conservation of energy. The stimulated emission and absorption of radiation both have close classical analogues. If a simple harmonic oscillator is driven by a sinusoidal electromagnetic field it can gain or lose energy depending on phase angles. The existence of spontaneous emission implies that all excited states of electrical systems are unstable and will eventually decay to the ground state by photon emission. Quantum systems thus comply with the fundamental principle that physical systems tend to seek out their state of lowest energy and maximum entropy.
In many practical cases a stationary system is perturbed in some way, inducing it to undergo transitions between the otherwise stationary states. Perhaps the best example concerns the radiative transitions of atomic electrons in which the disturbance of an external electromagnetic field causes the electrons to jump between energy levels, emitting or absorbing photons. Equation is a statement of the classical law of conservation of energy. The stimulated emission and absorption of radiation both have close classical analogues. If a simple harmonic oscillator is driven by a sinusoidal electromagnetic field it can gain or lose energy depending on phase angles. The existence of spontaneous emission implies that all excited states of electrical systems are unstable and will eventually decay to the ground state by photon emission. Quantum systems thus comply with the fundamental principle that physical systems tend to seek out their state of lowest energy and maximum entropy.
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.
Introduction The preceding chapters have focused on atomic transitions induced by applied radiation. That is, there is an optical field illuminating the atoms, and their response is calculated. It is implicitly assumed that an excited atom left alone will spontaneously return to the ground state, and conserve energy by emitting light that satisfies E 2 − E 1 = ħ ω 21 in accordance with the Planck and Bohr pictures. But this spontaneous emission process is not addressed quantitatively in these earlier chapters. Spontaneous emission is one of the most pervasive phenomena of atomic physics, and yet its origins remain among the least well-understood. The number of misconceptions is enormous, and they are to be found in textbooks, journal articles, and lecture notes. Because the natural decay of an excited atom adds energy to what is usually an empty mode of the electromagnetic field, the process is fundamentally quantum mechanical. Classical or even semi-classical descriptions cannot be assured to give correct answers. This is not to say that such discussion is to be avoided, but only that caution is needed in interpreting the results. Toward the end of the nineteenth century, many experimental results made it clear that classical mechanics needed to be supplemented by new theories. The first venture into the new physics was Planck's hypothesis that the energy of classical radiating oscillators like those discussed in Chap. 1 would have to be quantized into integer multiples of ħ ω. This notion led to his famous formula for the spectrum of thermal radiation from a non-reflective object (black body), and this formula describes a radiation field in thermodynamic equilibrium with its environment. The result of Planck's hypothesis in the context of thermal equilibrium plays a vital role in the discussion of spontaneous emission. Einstein A - and B -coefficients Soon after Bohr proposed a model of atomic structure consisting of discrete energy levels, connected by radiation whose energy satisfied Δ E = ħω when atoms made transition between them, Einstein published the first serious attempt to connect the absorption and emission processes. Absorption, he reasoned, could occur only in the presence of applied radiation, whereas spontaneous decay occurred without the application of any field.
So far we have treated the energy levels of an atomic system as stable states with infinite lifetimes. The presence of an electromagnetic field changes this picture. Absorption of photons will excite atoms and ions to higher levels, while stimulated emission will make excited ones decay. Einstein (1917) showed, using purely statistical arguments, that an excited ion will decay through spontaneous emission in the absence of an electromagnetic field. This process can also be derived by using a rigorous quantum electrodynamic treatment, where the field is quantized. In this chapter we start by discussing transitions between atomic levels in a general sense, postulating the operators responsible for the decay. After the first few sections we will concentrate on the most important few multipoles or terms in the expansion of the electromagnetic field. We will introduce a number of different properties describing the transition, and eventually arrive at the measurable transition rate and, directly linked to it, the lifetime of an excited state. We will start, however, with the most basic property, the component strength. Our aim is to arrive at computationally useful expressions as soon as possible. For a more thorough treatment of the theory of radiative transitions we refer to the book by Sobelman (1972). For a brief review of the many factors affecting spectra of atoms, see Martin and Wiese (1996) .
Some phenomena cannot be solved using the exact solution of the Schrödinger equation. However, using approximated methods such as perturbation theory we are able to obtain remarkable results considering terms up to second order. The physical phenomena studied here are the absorption and stimulated emission by the classical feature. In addition, we are going to discuss the physical meaning of perturbation theory when we treat the behaviour how initial state ket evolves as time goes on. We will evaluate the transition of probability between states, the rate and the energy involved in the atomic transitions. It will be introduced fundamental concepts of quantum mechanics, such as interaction picture, and a general perturbation theory using constant and sinusoidal time-dependent perturbation term. Concerning to these phenomena, we considered the perturbed term of the Hamiltonian of the interaction between the vector potential and electron momentum.
Most introductory courses on physics mention the basics of atomic physics: we learn about the ground state and excited states, and that the excited states have a finite life-time decaying eventually to the ground state while emitting radiation. You might have hoped for a better understanding of these decay processes when you started studying quantum mechanics. If this was the case, you must have been disappointed. Courses on basic quantum mechanics in fact assume that all quantum states have an infinitely long life-time. You learn how to employ the Schrödinger equation to determine the wave function of a particle in various setups, for instance in an infinitely deep well, in a parabolic potential, or in the spherically symmetric potential set up by the nucleus of a hydrogen atom. These solutions to the Schrödinger equation are explained as being stationary, the only time-dependence of the wave function being a periodic phase factor due to the energy of the state. Transitions between different quantum states are traditionally not discussed and left for courses on advanced quantum mechanics. If you have been disappointed by this, then this chapter will hopefully provide some new insight: we learn how matter and radiation interact, and, in particular, how excited atomic states decay to the ground state. Our main tool to calculate emission and absorption rates for radiative processes is Fermi’s golden rule (see Section 1.6.1). We thus start by refreshing the golden rule and specifying its proper use. Before we turn to explicit calculations of transition rates, we use the first part of the chapter for some general considerations concerning emission and absorption, those being independent of the details of the interaction between matter and electromagnetic radiation. In this context we briefly look at master equations that govern the probabilities to be in certain states and we show how to use those to understand properties of the equilibrium state of interacting matter and radiation. We show that it is even possible to understand so-called black-body radiation without specifying the exact interaction Hamiltonian of matter and radiation.