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Canadian Journal of Physics

The “accidental” degeneracy of the hydrogen atom is no accident

Pranawa C. Deshmukh, Aarthi Ganesan, N. Shanthi, Blake Jones, James Nicholson, Andrea Soddu

Published Aug 28, 2014• 5 citations
Publisher

Abstract

The Schrödinger equation does not account for the 2n2 degeneracy of the hydrogen atom, which it dismisses as an “accidental” degeneracy. The factor of “2” in the 2n2 degeneracy is well-accounted-for in the relativistic formulation by the two spin states of the electron. The n2 degeneracy is nevertheless not quite an “accident”; it is due to the SO(4), rather than SO(3), symmetry of the hydrogen atom. This result is well known, but is inadequately commented upon in most courses in quantum mechanics and atomic physics, leaving the student wondering about the origins of the n2 degeneracy of the hydrogen atom. A pedagogical analysis of this interesting aspect, which highlights the fundamental principles of quantum mechanics, is presented in this article. While doing so, not only is the n2 degeneracy of the hydrogen atom explained, but its energy spectrum and eigenfunctions are obtained without even using the Schrödinger equation, employing only the fundamental principles of quantum mechanics rather than the Schrödinger equation.

DOI
10.1139/cjp-2014-0300

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The Schrödinger equation does not account for the 2n2 degeneracy of the hydrogen atom, which it dismisses as an “accidental” degeneracy. The factor of “2” in the 2n2 degeneracy is well-accounted-for in the relativistic formulation by the two spin states of the electron. The n2 degeneracy is nevertheless not quite an “accident”; it is due to the SO(4), rather than SO(3), symmetry of the hydrogen atom. This result is well known, but is inadequately commented upon in most courses in quantum mechanics and atomic physics, leaving the student wondering about the origins of the n2 degeneracy of the hydrogen atom. A pedagogical analysis of this interesting aspect, which highlights the fundamental principles of quantum mechanics, is presented in this article. While doing so, not only is the n2 degeneracy of the hydrogen atom explained, but its energy spectrum and eigenfunctions are obtained without even using the Schrödinger equation, employing only the fundamental principles of quantum mechanics rather than the Schrödinger equation.
The Schrödinger equation is the cornerstone of quantum mechanics and is used to determine the energy levels of the hydrogen atom. However, in the teaching of Quantum Chemistry, many students tend to regard the solutions of the Schrödinger equation as purely mathematical results without fully understanding the physical origin of quantum energy levels. In this paper, an approximate model of the hydrogen atom is first developed based on the Heisenberg uncertainty principle and the Coulomb potential. This model is then used to derive the Bohr radius and the ground-state energy by minimizing the total energy function. Subsequently, the time-independent Schrödinger equation is formulated and solved by the method of separation of variables in spherical coordinates to obtain the exact energy spectrum of the hydrogen atom. The results demonstrate that both the approximate model and the exact solution predict the same ground-state energy, E1 = −13.6 eV, while the Schrödinger equation further generalizes this result to the quantized energy spectrum, En = −13.6/n2. These findings indicate that the solutions of the Schrödinger equation are not "miraculous" mathematical outcomes but rather the inevitable consequences of the fundamental principles of quantum mechanics. This approach provides a clearer physical interpretation of quantum energy levels and offers significant pedagogical value for the teaching of Quantum Chemistry.
A paradox has arisen from some recent treatments of accidental degeneracy which claim that, for three degrees of freedom, SU(3) should be a universal symmetry group. Such conclusions are in disagreement both with experimentally observed spectra and with the generally accepted solutions of Schrödinger's equation. The discrepancy occurs in the transition between classical and quantum-mechanical formulations of the problems, and illustrates the care necessary in forming quantum-mechanical operators from classical expressions. The hydrogen atom in parabolic coordinates in two dimensions, for which the traditional treatment of Fock, extended by Alliluev, requires the symmetry group O(3), is a case for which the newer methods of Fradkin, Mukunda, Dulock, and others require SU(2). Although these groups are only slightly different, SU(2) fails to be the ``universal'' symmetry group on account of the multiple-valuedness of the parabolic representation. This conclusion extends a result of Han and Stehle: that, for rather similar reasons, SU(2) cannot be the classical symmetry group for the two-dimensional hydrogen atom.
In the scientific community dominates the conviction that the hydrogen atom is the simplest, and existing theories based on equations of Schrodinger and Dirac fully describe all the subtleties of behavior of an electron in a hydrogen atom. In this paper and in the following articles will be shown that in addition to the known state-based solutions of the Schrodinger and Dirac equations, there are states which were not studied and they were not known, or often simply were discarded with the phrase have no physical meaning. Further it will be shown that the existing equations of quantum mechanics, namely the Dirac equation, Klein-Gordon equation and especially the Schrodinger equation, can not accurately describe all the subtleties of behavior of an electron in a hydrogen atom. As a result there will be given a reasonable basis for the feasibility of an experimental search or targeted synthesis of new unknown states of the hydrogen atom.
As the most basic and abundant atom in the universe, hydrogen atoms have long attracted the interest of scientists and provide the best subject for the exploration of quantum mechanics. This article provides a comprehensive study of the multifaceted characteristics and implications of the hydrogen atom. First, the research deeply studied the basic derivation of the Schrödinger equation of the hydrogen atom and provided the necessary theoretical framework. On this basis, modern computing tools are used to visualize the electron cloud of hydrogen atoms and reveal their shapes and characteristics under different orbits. In addition, the study investigated atomic transitions and associated spectra, elucidating basic quantum transition principles and serving as a benchmark for studying more complex atomic systems. Eventually, the research focus shifted to a specific direction, studying the Stark effect in hydrogen atoms, especially in the n=2 state. This research provides a novel perspective on understanding the fundamental properties of the hydrogen atom and its implications in modern physics research.