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Cambridge University Press eBooks

SPIN ET CETERA

Steven Weinberg

Published Nov 22, 2012• 0 citations
Publisher

Abstract

Wave mechanics failed badly in accounting for the multiplicity of atomic energy levels. This was most conspicuous in the case of the alkali metals, lithium, sodium, potassium, and so on. It was known that an atom of any of these elements can be treated as a more-or-less inert core, consisting of the nucleus and Z − 1 inner electrons, together with a single outer electron whose transitions between energy levels are responsible for spectral lines. Since the electrostatic field felt by the outer electron is not a Coulomb field, its energy levels in the absence of external fields depend on the orbital angular momentum quantum number ℓ as well as a radial quantum number n , but because of the spherical symmetry of the atom, not on the angular momentum z -component ħ m . (See Eq. (2.1.30).) For each n , ℓ , and m there should be just one energy level. But observations of atomic spectra showed that in fact all but the s states were doubled. For instance, even a spectroscope of low resolution shows that the D line of sodium, which is produced in a 3 p → 3 s transition, is a doublet, with wavelengths 5896 and 5890 Angstroms. Pauli was led to propose that there is a fourth quantum number for electrons in such atoms, in addition to n , ℓ , and m , with the fourth quantum number taking just two values in all but s states. But the physical significance of this fourth quantum number was obscure.

DOI
10.1017/cbo9781139236799.005

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Wave mechanics failed badly in accounting for the multiplicity of atomic energy levels. This was most conspicuous in the case of the alkali metals, lithium, sodium, potassium, and so on. It was known that an atom of any of these elements can be treated as a more-or-less inert core, consisting of the nucleus and Z − 1 inner electrons, together with a single outer electron whose transitions between energy levels are responsible for spectral lines. Since the electrostatic field felt by the outer electron is not a Coulomb field, its energy levels in the absence of external fields depend on the orbital angular momentum quantum number ℓ as well as a radial quantum number n , but because of the spherical symmetry of the atom, not on the angular momentum z -component ħ m . (See Eq. (2.1.30).) For each n , ℓ , and m there should be just one energy level. But observations of atomic spectra showed that in fact all but the s states were doubled. For instance, even a spectroscope of low resolution shows that the D line of sodium, which is produced in a 3 p → 3 s transition, is a doublet, with wavelengths 5896 and 5890 Angstroms. Pauli was led to propose that there is a fourth quantum number for electrons in such atoms, in addition to n , ℓ , and m , with the fourth quantum number taking just two values in all but s states. But the physical significance of this fourth quantum number was obscure.
Electron spin In our development of quantum mechanics to this point, the behavior of a particle, usually an electron, is governed by a wave function that is dependent only on the cartesian coordinates x, y, z or, equivalently, on the spherical coordinates r , θ, ϕ. There are, however, experimental observations that cannot be explained by a wave function which depends on cartesian coordinates alone. In a quantum-mechanical treatment of an alkali metal atom, the lone valence electron may be considered as moving in the combined field of the nucleus and the core electrons. In contrast to the hydrogen-like atom, the energy levels of this valence electron are found to depend on both the principal and the azimuthal quantum numbers. The experimental spectral line pattern corresponding to transitions between these energy levels, although more complex than the pattern for the hydrogen-like atom, is readily explained. However, in a highly resolved spectrum, an additional complexity is observed; most of the spectral lines are actually composed of two lines with nearly identical wave numbers. In an alkaline-earth metal atom, which has two valence electrons, many of the lines in a highly resolved spectrum are split into three closely spaced lines. The spectral lines for the hydrogen atom, as discussed in Section 6.5, are again observed to be composed of several very closely spaced lines, with equation (6.83) giving the average wave number of each grouping.
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.
In the introductory remarks to Chapter 5 mention was made of the 1925 proposal of Uhlenbeck and Goudsmit that to an electron there should be assigned an intrinsic angular momentum or spin S = (S x , S y , S z )—this in addition to its quantum angular momentum (or orbital angular momentum) M = (M x , M y , M z ) defined in (5.4.4). This is not to be taken to mean that an electron actually spins about an axis in some physical way. Experiments (in particular the noted Stern-Gerlach experiment) have provided adequate justification for the proposed concept of spin, a proposal also made by R. Bichowsky and H. Urey. Dirac has shown that the notion of spin is necessary if quantum mechanics and Einstein relativity are to be consistent theories. Chemical properties of atoms, and their ability to combine and form molecules, the splitting of spectral lines by a magnetic field applied to an atom (i.e., the Zeeman effect, which we discuss later), all depend on this important notion.
Abstract Bohr’s theory of the atom did a fine job of explaining the absorption and em1ss10n spectra of one-electron atoms in terms of the quantum rules. Schrodinger’s wave mechanics did better in the sense that the rules of quantization were given a firm mathematical basis. However, problems still abounded. Experimental spectra revealed quite a number of problems for which wave mechanics (and matrix mechanics) appeared to have no solutions. In particular, some atomic emission lines predicted by the theory were seen to be split in the presence of a magnetic field into several quite distinct lines (a phenomenon known as the Zeeman effect). Neither wave mechanics nor matrix mechanics could explain this phenomenon without some further, largely ad hoc, assumptions. Worse still, when the spectra of atoms with two or more electrons were studied, certain predicted lines were found to be missing.
The exclusion principle was the final outcome of Pauli's struggle to understand some spectroscopic anomalies in the early 1920s: doublets were observed in the spectra of alkali metals, singlets and triplets in the spectra of the alkaline earths, and even more anomalous patterns were observed when chemical elements were placed in an external magnetic field (anomalous Zeeman effect and Paschen–Back effect). These anomalous spectra challenged the old quantum theory, and prompted a radical theoretical change (Section 2.1). From 1920 to 1924 Alfred Landé, Werner Heisenberg, and Niels Bohr were all engaged in trying to save the traditional spectroscopic model (the so-called atomic core model) and to reconcile it with the observed anomalies. The impasse was solved only with Pauli's introduction of a fourth degree of freedom for the electron, and the consequent demise of the atomic core model (Section 2.2). What Pauli called the ‘twofoldness’ [ Zweideutigkeit ] of the electron's angular momentum was soon reinterpreted as the electron's spin (Section 2.3). Pauli's exclusion rule was announced in this semi-classical spectroscopic context that characterized the revolutionary transition from the old quantum theory to the new quantum theory around 1925. The prehistory of Pauli's exclusion principle Atomic spectra and the Bohr–Sommerfeld theory of atomic structure The existence of spectral lines had been known to scientists since the beginning of the nineteenth century when Wollaston and Fraunhofer first observed the dark absorption lines in the spectrum of the Sun.
This paper fully recognizes repeatable experimental facts related to atomic spectral observations electron shell arrangement and energy level transitions and respects all observed phenomena. It does not deny the statistical laws corresponding to energy level effects and the Pauli exclusion effect. The core purpose of this paper is to correct the long standing model inversion misunderstanding in quantum theory that is treating artificial definitions and mathematical approximation diagrams used by humans to simplify calculation and facilitate academic communication directly as physical reality in the microscopic world. This paper clearly distinguishes practical calculation rules from underlying physical mechanisms. Induced laws for human deduction and analysis cannot replace the true interaction nature of particles. This paper constructs a microscopic atomic picture based purely on mechanical balance with the core conclusions as follows. Atomic energy levels are not discrete geometric thin lines but continuous spherical potential energy intervals centered on atomic nuclei. The steady state of electron orbits arises from the combined balance of Coulomb repulsion and nuclear attraction instead of being preset in advance. The textbook diagrams showing intersecting orbits and dynamic avoidance of electrons are only effects of planar simplified drawing and do not represent the true microscopic state. Electrons in the same layer maintain stable equal spacing by Coulomb repulsion but spherical surfaces of inner and outer layers have different potential energy gradients leading to obvious differences in energy level gaps and finally differentiated transition spectra. Segmentation of visible light spectra originates from the difference in photoreception of cone cells in human eyes. Man is the measure of all things. Classification of spectra and energy levels by discrete criteria comes from human observational induction while natural ontology remains continuous. The Pauli exclusion effect is not an innate axiom of the universe but a natural mechanical result formed jointly by three dimensional space Coulomb repulsion and potential energy balance. This paper takes mechanical causality as the only main line to uniformly explain atomic energy levels spectral features and electron arrangement rules. All inferences strictly rely on experimental observations.