These results suggest that the natural width of a spectral line may be less than the value to be expected from the classical theory of damping by radiation.The subject of width of spectral line is one of considerable importance.If the lines are really much narrower than 0.12 X-Unit the radiation can- not come from a damped oscillating electron.The mechanism must be such as to maintain a pure harmonic oscillation of constant amplitude until the quantum of energy is completely emitted.Such a train of waves would need to have a great number of elements and so have considerable length.An alternate hypothesis would be that a quantum is an entity (the word "pulse" is avoided) that may be resolved into a train of waves by the crystal grating.In this case the width of a spectral line would de- pend on the degree of perfection of the crystal.The quantum theory of crystal grating action advanced by Duane8 might also give a narrow spec- tral line, whose width would be a property of the crystal grating and not of the radiation.
These results suggest that the natural width of a spectral line may be less than the value to be expected from the classical theory of damping by radiation.The subject of width of spectral line is one of considerable importance.If the lines are really much narrower than 0.12 X-Unit the radiation can- not come from a damped oscillating electron.The mechanism must be such as to maintain a pure harmonic oscillation of constant amplitude until the quantum of energy is completely emitted.Such a train of waves would need to have a great number of elements and so have considerable length.An alternate hypothesis would be that a quantum is an entity (the word "pulse" is avoided) that may be resolved into a train of waves by the crystal grating.In this case the width of a spectral line would de- pend on the degree of perfection of the crystal.The quantum theory of crystal grating action advanced by Duane8 might also give a narrow spec- tral line, whose width would be a property of the crystal grating and not of the radiation.
The correspondence principle postulates a relation between the average rate at which energy is actually being discontinuously emitted by quantum transitions and the continuous rate of emission which would be calculated from the classical theory. The principle has hitherto been used to predict the relative intensities of spectral lines of similar origin. Since, however, the classical theory permits a claculation of absolute rates of energy emission, it should be possible to calculate from the correspondence principle the absolute intensities of spectral lines. In the present article, the correspondence principle is subjected for the first time to this new kind of absolute test, using Czerny's data on the intensities of the far infra-red lines Nos. 8, 9, and 10 in the pure rotational spectrum of the dipole HCl. Tests of this kind have not previously been easy to make owing to lack of information as to the experimental values of absolute intensities or lack of knowledge of the the atomic models involved. The agreement between experimental and calculated intensities is close enough greatly to increase our confidence in the correspondence principle, justify us in subjecting it to further tests, and lead us to hope that an exact quantitative formulation of the principle may be found.
Abstract The new quantum mechanics could at first be used to answer questions concerning radiation only through analogies with the classical theory. In Heisenberg’s original matrix theory, for instance, it is assumed that the matrix elements of the polarisation of an atom determine the emission and absorption of radiation analogously to the Fourier components in the classical theory. In more recent theories a certain expression for the electric density obtained from the quantum mechanics is used to determine the emitted radiation by the same formulæ as in the classical theory. These methods give satisfactory results in many cases, but cannot even be applied to problems where the classical analogies are obscure or non-existent, such as resonance radiation and the breadths of spectral lines. A theory of radiation has been given by the author which rests on a more definite basis. It appears that one can treat a field of radiation as a dynamical system, whose interaction with an ordinary atomic system may be described by a Hamiltonian function. The dynamical variables specifying the field are the energies and phases of its various harmonic conrponents, each of which is effectively a simple harmonic oscillator. One must, of course, in the quantum theory take these variables to be q-numbers satisfying the proper quantum conditions. One finds then that the Hamiltonian for the interaction of the field with an atom is of the same form as that for the interaction of an assembly of light-quanta with the atom. There is thus a complete formal reconciliation between the wave and light-quantum points of view.
Atoms and ions containing residual bound electrons do not quite resemble the simple harmonic oscillator model used so successfully in the classical theory of radiation. However, replacing the atoms or ions with sets of harmonic oscillators of a great number of discrete resonance frequencies and having various amplitudes, together with the results of classical radiation theory, go a long way toward a quantitative description of emission or absorption spectra. The set of resonance frequencies is obtained from measured or calculated energy levels using Ritz's combination principle. The amplitudes are associated with matrix elements of appropriate quantum mechanical operators between wave functions of the two energy eigenstates involved at a given frequency. In other words, quantities of the emitters, absorbers, or scatterers are described quantum-mechanically, whereas the electromagnetic field is treated classically. Such semi-classical description of matter-electromagnetic field interactions became unnecessary very early in the development of quantum theory. It will therefore not be discussed in any detail. Instead, we will begin immediately with the combined theory of matter and radiation (Heitler 1954, Dirac 1958, Loudon 1983). Quantum theory of particles and fields There are various ways to also quantize the electromagnetic fields (Cohen-Tannoudji, DuPont-Roc and Grynberg 1989), of which that performed on the combined Hamiltonian equations of motion for the field-matter system is followed here.
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.
The quantum theory of radiation, formulated in wave-mechanical language but in terms of running waves, is shown to lead under suitable conditions to the classical theory of emission by a particle as a first approximation. Non-relativistic mechanics is used, and the limitations of the method are brought out in terms of classical theory. The characteristic quantum phenomenon of the Compton effect requires that the Compton recoil shall exceed the spread in momentum of the particle, and so that the wave-packet shall greatly exceed in diameter the wave-length of the incident radiation; this condition is realizable on any scale of magnitude. For quasi-classical motion just the reverse is required; furthermore, if the motion is to last for a number of waveperiods, the wave-length must greatly exceed mch (m=massoftheparticle). The classical packet-motion arises from combinations between quantum-states of the particle-field system; this fact suggests that the photon is not a fundamental constituent of the field but only one possible aspect of its action. The infinite "zero-energy" associated apparently even with the lowest energy-state of the field implies no electromagnetic field intensities at any point. Whereas for problems on energy or momentum it is customary to represent an incident wave-train by a single typical quantum state, to obtain motional phenomena of classical type a more complete expression such as that given in the paper must be used. The physically empty field likewise corresponds to a mixture of quantum states but without correlation among their amplitudes.
An attempt is made to present a consistent detailed theory of optical phenomena, based on the suggestion recently made by the author in collaboration with Bohr and Kramers. This suggestion is that atoms are radiating or absorbing continuously, during their stationary states, and that transitions influence radiation only in terminating the radiation characteristic of the old state, and substituting that of the new. The atoms, on the other hand, are supposed not to change their energy while radiating, but to change it discontinuously on transition. This necessitates giving up the detailed application of the conservation of energy in interaction between atoms and radiation. In the present paper, an additional suggestion is made, namely that resonance radiation is to be identified with the radiation carried out by the spherical wavelets which, by their interference with the external field, also produce absorption. This is practically a return to the classical picture of resonance radiation. Statement of the theory consists formally of two parts: the description of the behavior of atoms, and of radiation, when the two interact. The first involves the statement of the probabilities of transition of atoms, and is taken without change from Einstein. The probability of interruption of coherent vibrations is also discussed. The second requires the specification of the fields emitted by atoms in any steady state under the influence of any external field. These consist of spherical wavelets of the frequencies of the various quantum lines which the atom can emit or absorb in the stationary state in which it is. For emission frequencies, wavelets are emitted even in the absence of an external field; for absorption frequencies, external fields induce wavelets, similar to the wavelets of linearly bound electrons in electron theory, which on the one hand interfere with the external field to produce the phenomena of dispersion, etc., and on the other carry out the resonance radiation in all directions. Detailed descriptions of these fields are given. In a discussion of the theory, it is first shown that the assumptions which have been made about the field satisfy the correspondence principle, in that for large quantum numbers the field aproaches that which would be emitted classically on account of the interaction of an external field and a multiply periodic atom. On the other hand, it is shown that the field has a character essentially like that of classical electron theory, which is known to be in general agreement with experiments. Next, the energy and momentum relations at interaction of atoms and light are investigated, and it is shown that, although these quantities are not precisely conserved, still the assumptions as to atomic and radiation processes have been so made that they are conserved on an average over a great number of atomic processes. Finally the spectral resolution of emitted and absorbed radiation is considered; the theory gives a minimum breadth for the lines, depending on the finite length of wave trains resulting from the finite life in stationary states, and it is shown that Kirchhoff's law is obeyed, the emission and absorption lines being of the same breadth. By way of illustration, specific application of the theory is made to the simple examples of emission of light by bombardment of electrons at the resonance potential, resonance radiation, its quenching by presence of foreign gases, absorption, scattering, and disperison.