The paper gives an account of the author's work on a new form of quantum theory. \textsection{}1. The Hamiltonian analogy between mechanics and optics. \textsection{}2. The analogy is to be extended to include real "physical" or "undulatory" mechanics instead of mere geometrical mechanics. \textsection{}3. The significance of wave-length; macro-mechanical and micro-mechanical problems. \textsection{}4. The wave-equation and its application to the hydrogen atom. \textsection{}5. The intrinsic reason for the appearance of discrete characteristic frequencies. \textsection{}6. Other problems; intensity of emitted light. \textsection{}7. The wave-equation derived from a Hamiltonian variation-principle; generalization to an arbitrary conservative system. \textsection{}8. The wave-function physically means and determines a continuous distribution of electricity in space, the fluctuations of which determine the radiation by the laws of ordinary electrodynamics. \textsection{}9. Non-conservative systems. Theory of dispersion and scattering and of the "transitions" between the "stationary states." \textsection{}10. The question of relativity and the action of a magnetic field. Incompleteness of that part of the theory.
The paper gives an account of the author's work on a new form of quantum theory. \textsection{}1. The Hamiltonian analogy between mechanics and optics. \textsection{}2. The analogy is to be extended to include real "physical" or "undulatory" mechanics instead of mere geometrical mechanics. \textsection{}3. The significance of wave-length; macro-mechanical and micro-mechanical problems. \textsection{}4. The wave-equation and its application to the hydrogen atom. \textsection{}5. The intrinsic reason for the appearance of discrete characteristic frequencies. \textsection{}6. Other problems; intensity of emitted light. \textsection{}7. The wave-equation derived from a Hamiltonian variation-principle; generalization to an arbitrary conservative system. \textsection{}8. The wave-function physically means and determines a continuous distribution of electricity in space, the fluctuations of which determine the radiation by the laws of ordinary electrodynamics. \textsection{}9. Non-conservative systems. Theory of dispersion and scattering and of the "transitions" between the "stationary states." \textsection{}10. The question of relativity and the action of a magnetic field. Incompleteness of that part of the theory.
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.
Chapter 4 deals with Quantum Mechanical (QM) phenomena. The first section describes the first attempts at quantization of energy, momentum, angular momentum, etc. We start with Plank's solution to the black-body problem, introducing the concept of photons: discrete packets of electromagnetic energy. We show how Plank's description of black-body radiation is perfectly fit by the cosmic microwave radiation, providing the strongest evidence for the Big-Bang at the origin of the Universe. We then describe Bohr's solution to the paradoxical stability of atoms, introducing quantization of angular momentum (or action) and correctly predicting the energy levels of the hydrogen atom. We show how Einstein used Plank's idea to explain the photo-electric effect (an effect exploited in CCD cameras and solar cells) and how he used Bohr's understanding of energy levels in atoms to provide an intuitive explanation of Plank's law. Einstein insight opened the way to the field of spectroscopy and the development of the laser. In the second section, following the lead of Dirac, we show that QM is equivalent to Linear Algebra in the space of complex functions (which describe the state of the system). We show that Schrödinger's equation is a natural consequence of that description, once the relation between energy and frequency established by Plank (for photons) and de Broglie (for particles) is taken into account. In the context of the chiral ammonia molecule we discuss the queerness of QM which describes physical systems as superposition of states (such as left and right chirality state of a molecule, dead and alive cat). We show that this queerness is nonetheless supported by experiments and is behind much of our technology: masers and lasers, atomic clocks, semiconductors (diodes, transistors, etc.). In the following section we introduce the representation of operators in QM (the equivalent of matrices in linear algebra): momentum, position, energy, etc. which correspond to measurements on the system. We show that the non-commutability of some operators (common with matrix operations) leads to Heisenberg uncertainty principle: the position and momentum of a particle cannot be determined with absolute precision. We discuss the solution of Schrödinger's equation for free particles demonstrating their equivalence with EM phenomena: particles undergo refraction and diffraction, exemplifying the particle/wave duality inherent to QM systems. We discuss QM tunneling and its use in the Scanning Tunneling Microscope. In the following section we study Dirac's equation: the successful attempt by Dirac to unify QM with Einstein's relativity, with the resulting prediction of anti-particles and spin. We then solve for the energy levels of electrons in the hydrogen atom (from Schrödinger's equation) and show that the existence of spin profoundly affects the behavior of electrons in an atom: they cannot share the same energy level, a rule known as Pauli's exclusion principle. Pauli's principle is central to the understanding of the chemical properties of atoms and fully explains Mendeleev's periodic table of the elements. In the next section we discuss along with two exactly soluble systems (diatomic rotational and vibrational levels), various approximations used to study systems (e.g. molecules) for which there are no analytical solutions. In particular, we introduce Pauling's variational approach, Hückel molecular orbital theory and time independent perturbation theory. We apply those approaches to determine the energy levels in alkenes, in multi-electron atoms and in systems under constant electric or magnetic field (such as in Magnetic Resonance Imaging). In the last section we discuss time dependent perturbation theory. We use it to establish the rules allowing for transitions between energy levels and revisit Einstein description of absorption/emission phenomena.
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.
Abstract It is well known that the experimental facts of atomic physics necessitate a departure from the classical theory of electrodynamics in the description of atomic phenomena. This departure takes the form, in Bohr’s theory, of the special assumptions of the existence of stationary states of an atom, in which it does not radiate, and of certain rules, called quantum conditions, which fix the stationary states and the frequencies of the radiation emitted during transitions between them. These assumptions are quite foreign to the classical theory, but have been very successful in the interpretation of a restricted region of atomic phenomena. The only way in which the classical theory is used is through the assumption that the classical laws hold for the description of the motion in the stationary states, although they fail completely during transitions, and the assumption, called the Correspondence Principle, that the classical theory gives the right results in the limiting case when the action per cycle of the system is large compared to Planck’s constant h, and in certain other special cases. In a recent paper Heisenberg puts forward a new theory, which suggests that it is not the equations of classical mechanics that are in any way at fault, but that the mathematical operations by which physical results are deduced from them require modification. All the information supplied by the classical theory can thus be made use of in the new theory.
Let us return from optics to mechanics and explore the analogy to its fullest extent. In optics the old system of mechanics corresponds to intellectually operating with isolated mutually independent light rays. The new undulatory mechanics corresponds to the wave theory of light . Erwin Schrödinger, Nobel lecture , 1933 In this chapter we shall see that electromagnetic waves and electrons feature a number of common properties under conditions of spatial confinement. Simple and familiar problems from introductory quantum mechanics and textbook wave optics are recalled in this chapter to emphasize the basic features of waves in spatially inhomogeneous media. Herewith we make a first step towards understanding the properties of electrons and electromagnetic waves in nanostructures and notice that these properties in many instances are counterparts. Different formulas and statements of this chapter can be found in handbooks on quantum mechanics and wave optics. A few textbooks on quantum mechanics do consider analogies of propagation and reflection phenomena in wave optics with those in wave mechanics. Isomorphism of the Schrödinger and Helmholtz equations In Chapter 2 we discussed that an electron in quantum mechanics is described by the wave function, the square of its absolute value giving the probability of finding an electron at a specific point in space. This function satisfies the Schrödinger equation (2.56) which is the second-order differential equation with respect to space and the first-order differential equation with respect to time.
Bohr's 1913 trilogy marks a turning point in the history of quantum physics for its introduction of the planetary model of the atom and its derivation of the Balmer formula for the hydrogen spectrum. It has been studied in the seminal study 1 and is discussed more recently by 2-4. Famously, Bohr's classical paper made two utterly non-classical assumptions, according to which electrons orbited the nucleus in stationary states without losing energy while they emitted radiation only in transitions between these states. As I will argue in this paper, Bohr's 1913 trilogy made a third crucial major assumption, which entailed key elements of the correspondence principle formulated five years later. This third assumption postulated a relation between the mechanical frequency of a stationary state and the radiation frequency in analogy with classical radiation theory. Though this relation was in direct conflict with the key assumptions of stationary states and transitions, Bohr's reasoning—as I want to show—relied heavily on it, and a major part of his initial work was devoted to clarifying how the connection of radiation and motion, the stationary states and the transitions were interrelated. The main aim of Bohr's 1913 trilogy was to derive the Balmer formula from the newly-proposed atomic model. After the introduction of the stationary states and the frequency condition, the derivation follows a three-step recipe consisting of the calculation of the energy from classical mechanics, the quantization of the energy and finally the calculation of the spectral frequencies via the Planck Relation . Given the simplicity of the system considered and the assumption of the stationary states and the frequency condition, the first and last step did not call for an extended argument and Bohr simply gave the relevant equations. As Bohr explicitly acknowledged, the classical radiation mechanism was replaced entirely by the fundamental assumptions of his model: radiation is produced through a transition between stationary states. Though 1 was in direct conflict with the physical assumptions of his model, Bohr's thinking nonetheless depended crucially on it. This is emphasized by the fact that Bohr knew that he could quantize the orbits on the assumption that the angular momentum of the atom is equal to .1 While 1 could not be interpreted as a description of a physical process in a classical sense, Bohr kept the equation and explored its conceptual significance within his new quantum theory of the atom. This was a vital concern for Bohr, first, because he needed a justification; second, because he hoped for insights on how to develop the theory by investigating which parts of classical radiation theory could still be used within the new model. The investigation of this question loomed large in Bohr's 1913 paper and continued to play an important role in his early work on the quantum theory of the atom. For the preceding argument Bohr justified the radiation-motion relation by means of a comparison between the radiation process and the motion of the electron before and after the radiation process. This justification itself was not very convincing: it rested solely on its empirical success and the questionable mean-value argument, and Bohr decided to give a second derivation of the Balmer formula to add further plausibility to 1. Already his first hand waving argument, however, points to some of the central aspects of his attempt to connect radiation and electronic motion: In light of the missing radiation mechanism in quantum theory, Bohr tried to recover a relation between radiation and electronic motion within quantum theory analogous to the one in classical radiation theory. He refrained from proposing a new hypothetical radiation mechanism and shied away from such assumptions until 1924. Instead he resorted to experimental, mathematical and intertheoretical arguments to construct a formal relation between radiation and matter and aimed to get insights into the properties of a radiation mechanism yet to be found. In order to be equivalent to the empirical Balmer formula this function has to be , as Bohr showed by comparing the frequency of a quantum transition and the orbiting frequencies of the stationary states in the case of high quantum numbers, in which classical electrodynamics and quantum theory predict the same numerical value for the radiation frequency. This result implied the consistency of his major assumptions, the radiation-motion connection and the Balmer formula, which entered as an empirical constraint. For the argument the high quantum number limit plays an important role as it renders the condition for the consistency precisely and shows that the assumption of a relation between radiation and motion within quantum theory leads to the agreement of quantum theory and classical theory in this limit. The possibility of an emission of a radiation of such a frequency may also be interpreted from analogy with ordinary electrodynamics, as an electron rotating round a nucleus in an elliptical orbit will emit a radiation which according to Fourier's theorem can be resolved into homogeneous components, the frequencies of which are [5, 14]. This recapturing of the relation between orbital frequency and the radiation frequency is part of Bohr's conclusion: While classical electrodynamics in general is in contradiction with the basic assumptions of the Bohr model, the classical relation between the frequency of radiation and the mechanical frequency can be established at least in the classical limit as a formal relation. To show this is as important to Bohr as to show that his new model predicts the correct Balmer formula. As such the classical relation between motion and radiation is indispensable for Bohr's early work as a touchstone for his two derivations and it is of vital concern in the attempt to explore the break and the continuity with classical radiation theory. The radiation-motion relation continued to play an important role in Bohr's works following the 1913 trilogy; after he had finished his initial papers Bohr adapted his model to account for the Stark and Zeeman effects. The relation between radiation and motion played a major role in the initial work establishing the Bohr model and its extension to the Stark and Zeeman effect. Stemming from classical radiation theory this relation was in contradiction with the major assumptions of the new model of the atom; nonetheless, Bohr's thinking relied heavily on the radiation-motion connection both in establishing his results and in clarifying the foundations of the new model. Compared with his later statements on the correspondence principle there is a remarkable resemblance between the statements in 1913/1914 and the correspondence idea between 1918 and 1923: In both cases the relation between the orbiting frequency and the frequency of radiation and the asymptotic limit between quantum theory and classical electrodynamics were at the core of Bohr's reasoning. Also the idea of the Fourier series is mentioned, which would become ever more important in the development of the correspondence idea.5 While the core elements of the later principle are already apparent in the early phase, they are used very differently in both phases. This shift in the usage of the basic correspondence relation was due to the development of the quantum theory of the atom as a whole. The physicists who developed Bohr's initial model mainly extended the description of the stationary states to more complicated systems with the help of celestial mechanics. In this context the relation between the radiation frequency and the orbiting frequency was replaced by Sommerfeld's quantum condition: . The new relation did not involve any assumptions on the radiation process or the interaction between radiation and matter, it was a statement about the action of a mechanical system and its quantization. The fruitfulness of this new quantization condition led physicists including Bohr to abandon the early quantization procedure. Through this abandonment, the frequency condition became the sole relation of radiation theory, which was needed to determine the series formulae describing atomic spectra. Whereas the loss of the classical radiation mechanism had been a vital concern for Bohr in his early works, this was no longer the case in the development of the quantum theory of the atom. The relation should, however, resurface in Bohr's thinking about the transitions in quantum theory and in this form led to the formulation of the correspondence principle.