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Cambridge University Press eBooks

Absorption of radiation

Lorenzo J. Curtis

Published Oct 30, 2003• 0 citations
Publisher

Abstract

Backward, turn backward, O time in your flight. Make me a child again, just for tonight. –Elizabeth Akers Allen Since the time of Kirchhoff it has been known that, when light is passed through an atomic gas, those wavelengths are observed that would be emitted if the gas were incandescent. If the gas is sufficiently cold, then the wavelengths observed are limited to ground-state transitions. As the temperature of the sample is elevated, wavelengths corresponding to transitions between excited states become absorbing, and balances between emission and absorption occur. The study of the central wavelengths of emission lines or absorption notches is known as first-order spectroscopy, and it provides information on the energy-level structure of the atom. The study of the shape of these lines in frequency space is known as second-order spectroscopy, and provides information on the lifetime of the level and the collision rates and temperature of the gas. Thus, whereas first-order spectroscopy shows that emission and absorption measurements yield the same central wavelengths, second-order spectroscopy shows that the natural linewidth for emission and absorption are both specified by the level lifetime, and that the intensity of emission and absorption features both involve the linestrength factor (through the emission transition probability rate and the absorption oscillator strength). The connection between the lifetime and the linewidth can be made plausible by a simple semiclassical model. When an electron is excited to a specific orbit in an atom, its binding energy is established through the exchange of virtual photons with the effective central core. If the perturbations that eventually cause the electron to make a transition from that orbit are weak, the meanlife will be long.

DOI
10.1017/cbo9780511755552.010

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Cambridge University Press eBooks•Feb 20, 2018•0 citations
Backward, turn backward, O time in your flight. Make me a child again, just for tonight. –Elizabeth Akers Allen Since the time of Kirchhoff it has been known that, when light is passed through an atomic gas, those wavelengths are observed that would be emitted if the gas were incandescent. If the gas is sufficiently cold, then the wavelengths observed are limited to ground-state transitions. As the temperature of the sample is elevated, wavelengths corresponding to transitions between excited states become absorbing, and balances between emission and absorption occur. The study of the central wavelengths of emission lines or absorption notches is known as first-order spectroscopy, and it provides information on the energy-level structure of the atom. The study of the shape of these lines in frequency space is known as second-order spectroscopy, and provides information on the lifetime of the level and the collision rates and temperature of the gas. Thus, whereas first-order spectroscopy shows that emission and absorption measurements yield the same central wavelengths, second-order spectroscopy shows that the natural linewidth for emission and absorption are both specified by the level lifetime, and that the intensity of emission and absorption features both involve the linestrength factor (through the emission transition probability rate and the absorption oscillator strength). The connection between the lifetime and the linewidth can be made plausible by a simple semiclassical model. When an electron is excited to a specific orbit in an atom, its binding energy is established through the exchange of virtual photons with the effective central core. If the perturbations that eventually cause the electron to make a transition from that orbit are weak, the meanlife will be long.
Abstract Since the beginning of this century we have a rough understanding about the structure of atoms. They consist of a nucleus and electrons orbiting around this nucleus. We know that electrons occupy only certain discrete energy states. When they decay from a high-energy state to a low-energy state, they emit electromagnetic radiation. Usually, the low-energy state will be the ground state. In that case, the emitted radiation is called resonance radiation.1 Since the resonance photons have an energy that corresponds to the energy of the transition, they can easily be absorbed by other ground-state atoms. A ground-state atom that absorbs the resonance photon is excited to the upper state for some time and will eventually release the photon again. This absorption/reemission process can be repeated many times, until the photon finally escapes from the vapour. This process is called ‘radiation trapping’ (also known as ‘imprisonment of resonance radiation’, ‘radiative transfer of spectral lines’, ‘line transfer’, or ‘radiation diffusion’).
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.
Introduction Series of atomic spectral lines had been studied by emission from excited vapors even before Balmer described the regularity of the visible lines of hydrogen in 1884. However, direct excitation had been restricted to the few lowest-lying levels, particularly those accessible by electric dipole transitions from the ground state using classical light sources. The advent of tunable lasers in the 1970s changed such spectroscopic limitations enormonsly, allowing excitation to a very much larger number of states. Atoms in highly excited states, typically with principal quantum numbers n ≥ 10, are called Rydberg atoms. They are oversize, fragile states of significant intrinsic interest. They are very rare in nature because of their size and fragility, but they are found in interstellar space (H I regions). One of the best sources for comprehensive descriptions of Rydberg atoms and references to the literature describing their exploration is Ref. [120]. It describes their characteristic properties and behavior both classically and quantum mechanically, and especially their strongly enhanced interactions with external fields. The first thing to note is that Rydberg atoms are usually characterized by a single, highly excited electron while all the other electrons remain in their original states. Thus their properties are very nearly classical, and the atoms are much closer to the ideal hydrogen-like model of Chap. 7, along with appropriate quantum defects (see Chap. 10). The spectroscopy of such states is especially interesting because the active electron is much less perturbed by the other electrons in the atom than when it is in lower states. Moreover, there are some special circumstances in which the energy of a Rydberg state is degenerate with an atomic state having two electrons excited to lower levels, and such configurations yield further new information. Second, Rydberg atoms do not usually decay back to the ground state by emission of characteristic radiation, so their study is mediated by other techniques that reveal new and interesting properties. Such properties arise because Rydberg atoms have a huge dipole moment and very low binding energy resulting from the large average distance between the excited electron and the nucleus-plus-core of the rest of the atom with net charge e . Third, transitions between Rydberg states are quite different from those connecting to the ground state for at least three reasons.
Lux aeterna luceat eis. Let there be light. Take the rest of the week off. Atomic energy levels deduced from optical spectra comprise one of the most precisely known sets of physical measurements that exist. However, the precision of the determinations of the relative oscillator strengths of these spectral lines from the relative intensities of spectral lines is much less precise. Fortunately, time-dependent methods for the study of the dynamics of the emission process exist (and are being developed) that permit the transition probability rates, oscillator strengths, and reaction rates to be determined with ever-increasing precision. In most elementary quantum mechanics textbooks, the section on the emission of radiation is the least satisfactory section of the book. Whereas the development of relationships among various spatial overlap integrals between state vectors for various operators (such as the electrostatic dipole moment) can be formulated in a very elegant ab initio manner, the connection of these matrix elements to the time dependence of the system often seems driven by a posteriori assumptions that are extended beyond their justifiable range of applicability. As Fermi observed in stating his Golden Rule , “the transition probability and energy perturbation can be calculated with the help of perturbation theory ( i.e. , there is no better way known).” The Weisskopf–Wigner approximation offers a scheme for making precise calculations, but does not provide the rigor that has characterized so many other areas of quantum mechanics.
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) .
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.