The largest failure of the old, Bohr-Sommerfeld quantum theory was with the helium atom. It brought about the theory's demise. I show that this failure does not originate, as commonly believed, with the orbit concept per se. Instead, it was caused by the wrong choice of orbits, compounded by ignorance of the exclusion principle. Choosing semiclassical electron oscillations through the He nucleus, I calculate a singlet ground-state energy that rivals in accuracy with quantum-mechanical results. The same method reveals Bohr's historic energy value as the forbidden triplet ground state--a result beyond the reach of quantum mechanics. At the qualitative level, the concept of Coulomb oscillations visually explains the major features in the He double spectrum in terms of crossed or parallel orbit orientation.
The largest failure of the old, Bohr-Sommerfeld quantum theory was with the helium atom. It brought about the theory's demise. I show that this failure does not originate, as commonly believed, with the orbit concept per se. Instead, it was caused by the wrong choice of orbits, compounded by ignorance of the exclusion principle. Choosing semiclassical electron oscillations through the He nucleus, I calculate a singlet ground-state energy that rivals in accuracy with quantum-mechanical results. The same method reveals Bohr's historic energy value as the forbidden triplet ground state--a result beyond the reach of quantum mechanics. At the qualitative level, the concept of Coulomb oscillations visually explains the major features in the He double spectrum in terms of crossed or parallel orbit orientation.
The old quantum theory of Bohr and Sommerfeld was abandonned for the wrong reason. Its contradictions were caused not by the orbit concept but by a mental barrier--the inconceivability that an electron might collide with the atomic nucleus. Removing that barrier resolves the theory's main failures--incorrect orbital momenta, He atom, H2+ molecule ion. The inclusion of electron oscillations through the nucleus--a concept called "Coulomb oscillator"--renders the old quantum theory consistent with quantum mechanics (although devoid of wave character). The triple success of the Bohr-Sommerfeld model is its correct description of the H atom (and one-electron ions) concerning (1) the energy levels Enl, (2) the orbital angular momenta Lnl--if corrected as Lnl^2 = l(l+1) hbar^2 and with the Coulomb oscillator included--and (3) the orbits' space quantization--with (Lnl)z = ml hbar. These achievements are succinctly represented by the principal, angular and magnetic quantum numbers (n, l, ml) and visualized by orbital ellipse geometry--major axis, vertex curvature, and tilt angle, respectively. Orbit geometry also accounts for the average orbit size. Moreover, the Coulomb oscillator provides a natural explanation of (isotropic) hyperfine interaction. The shortcomings of the old quantum theory lie in its neglect of three properties of particles--their spin, their wave nature and their quantum statistics. These deficiencies notwithstanding, the visual appeal of the Bohr-Sommerfeld model remains a pedagogical asset to complement the abstract character of quantum mechanics.
The old quantum theory of Bohr and Sommerfeld was abandonned for the wrong reason. Its contradictions were caused not by the orbit concept but by a mental barrier—the inconceivability that an electron might collide with the atomic nucleus. Removing that barrier resolves the theory’s main failures—incorrect orbital momenta, He atom, H + 2 molecule ion. The inclusion of electron oscillations through the nucleus—a concept called “Coulomb oscillator”—renders the old quantum theory consistent with quantum mechanics (although devoid of wave character). The triple success of the Bohr-Sommerfeld model is its correct description of the H atom (and one-electron ions) concerning (1) the energy levels Enl, (2) the orbital angular momenta Lnl—if corrected as L 2 = l(l + 1)~ 2 and with the Coulomb oscillator included—and (3) the orbits’ space quantization—with (Lnl)z = ml~. These achievements are succinctly represented by the principal, angular and magnetic quantum numbers (n, l, ml) and visualized by orbital ellipse geometry—major axis, vertex curvature, and tilt angle, respectively. Orbit geometry also accounts for the average orbit size. Moreover, the Coulomb oscillator provides a natural explanation of (isotropic) hyperfine interaction. The shortcomings of the old quantum theory lie in its neglect of three properties of particles—their spin, their wave nature and their quantum statistics. These deficiencies notwithstanding, the visual appeal of the Bohr-Sommerfeld model remains a pedagogical asset to complement the abstract character of quantum mechanics.
Bohr's atomic theory is widely viewed as remarkable, both for its accuracy in predicting the observed optical transitions of one-electron atoms and for its failure to fully correspond with current electronic structure theory. What is not generally appreciated is that Bohr's original semiclassical conception differed significantly from the Bohr-Sommerfeld theory and offers an alternative semiclassical approximation scheme with remarkable attributes. More specifically, Bohr's original method did not impose action quantization constraints but rather obtained these as predictions by simply matching photon and classical orbital frequencies. In other words, the hydrogen atom was treated entirely classically and orbital quantized emerged directly from the Planck-Einstein photon quantization condition, E = h nu. Here, we revisit this early history of quantum theory and demonstrate the application of Bohr's original strategy to the three quintessential quantum systems: an electron in a box, an electron in a ring, and a dipolar harmonic oscillator. The usual energy-level spectra, and optical selection rules, emerge by solving an algebraic (quadratic) equation, rather than a Bohr-Sommerfeld integral (or Schroedinger) equation. However, the new predictions include a frozen (zero-kinetic-energy) state which in some (but not all) cases lies below the usual zero-point energy. In addition to raising provocative questions concerning the origin of quantum-chemical phenomena, the results may prove to be of pedagogical value in introducing students to quantum mechanics.
Abstract We consider three topics which proved frustratingly resistant to the methods of the old quantum theory up to the point of emergence of the quantum mechanics of Heisenberg and collaborators in late 1925. First, the old theory could not account convincingly for the superfluity of stationary states implied by the existence of the complex multiplets seen in most atomic spectra. Second, the progressively more complicated theories proposed for explaining the splittings of lines in the anomalous Zeeman effect were found to lead inevitably to glaring inconsistencies with the assumed mechanical equations of motion. Finally, there was the problem of the dual spectrum of helium, and even more basically, of the ground state energy of helium, all calculations of which in terms of specified electron orbits gave incorrect results. We relate the tangled history of the efforts to provide a theoretical resolution of these problems within the old quantum theory.
Models for the Helium Atom.---(1) Bohr's model is unsatisfactory because it gives too great a value for the ionizing potential and is not in accord with the optical and magnetic properties of helium. Now the chemical evidence suggests that each electron in an atom has its own separate orbit, and that these orbits are closely interrelated. Accordingly two new models are considered. (2) In the double circle model the two electrons are assumed to move in two separate, parallel, circular orbits. The model, however, is unstable, for the ionizing potential, computed by applying the quantum theory, comes out negative. Another objection is that the magnetic moment is not zero. (3) In the semi-circular model each electron is assumed to oscillate back and forth along an approximately semi-circular path in accord with classical mechanics, each being brought to rest at the end of its path by the repulsion of the other. Assuming the maximum angular momentum of each equal to $\frac{h}{2\ensuremath{\pi}}$, the absolute dimensions of the model were computed. The total energy comes out less than for the Bohr model, and the ionizing potential, 25.62 volts, agrees closely with the experimental value. The magnetic moment is zero.Application of the Quantum Theory to Coupled Electrons.---The success of the semi-circular model in giving the correct value for the ionizing potential of helium suggests that in the case of coupled electrons the quantum theory should be applied not to the momentum of the individual electrons according to the relation $\ensuremath{\int}\mathrm{pdq}=\frac{h}{2\ensuremath{\pi}}$, but rather to the momentum which, by being relayed from one electron to another, passes in each direction around the nucleus.
Models for the Helium Atom.---(1) Bohr's model is unsatisfactory because it gives too great a value for the ionizing potential and is not in accord with the optical and magnetic properties of helium. Now the chemical evidence suggests that each electron in an atom has its own separate orbit, and that these orbits are closely interrelated. Accordingly two new models are considered. (2) In the double circle model the two electrons are assumed to move in two separate, parallel, circular orbits. The model, however, is unstable, for the ionizing potential, computed by applying the quantum theory, comes out negative. Another objection is that the magnetic moment is not zero. (3) In the semi-circular model each electron is assumed to oscillate back and forth along an approximately semi-circular path in accord with classical mechanics, each being brought to rest at the end of its path by the repulsion of the other. Assuming the maximum angular momentum of each equal to $\frac{h}{2\ensuremath{\pi}}$, the absolute dimensions of the model were computed. The total energy comes out less than for the Bohr model, and the ionizing potential, 25.62 volts, agrees closely with the experimental value. The magnetic moment is zero.Application of the Quantum Theory to Coupled Electrons.---The success of the semi-circular model in giving the correct value for the ionizing potential of helium suggests that in the case of coupled electrons the quantum theory should be applied not to the momentum of the individual electrons according to the relation $\ensuremath{\int}\mathrm{pdq}=\frac{h}{2\ensuremath{\pi}}$, but rather to the momentum which, by being relayed from one electron to another, passes in each direction around the nucleus.