The quantum mechanics of two-electron systems is reviewed, starting with the ground state of the helium atom and heliumlike ions with central charge Z. The case of Z≥2 is rather straightforward. In contrast, for negative hydrogen ion with Z=1, the stability of H− cannot be achieved using a product of individual electron wavefunctions and requires explicit account of the anticorrelation among the two electrons. The wavefunction proposed by Chandrasekhar is revisited, where the permutation symmetry is first broken and then restored by a counterterm. More difficult problems can be studied using the same strategy such as the stability of hydrogenlike ions for any value of the proton-to-electron mass ratio M/m, the energy of the lowest spin-triplet state of helium and heliumlike ions, and the stability of the doubly excited hydrogen ion with unnatural parity. The positronium molecule, which was predicted years ago and discovered recently, can also be shown to be stable against spontaneous dissociation. Emphasis is placed on symmetry breaking, which can either spoil or improve the stability.
The quantum mechanics of two-electron systems is reviewed, starting with the ground state of the helium atom and heliumlike ions with central charge Z. The case of Z≥2 is rather straightforward. In contrast, for negative hydrogen ion with Z=1, the stability of H− cannot be achieved using a product of individual electron wavefunctions and requires explicit account of the anticorrelation among the two electrons. The wavefunction proposed by Chandrasekhar is revisited, where the permutation symmetry is first broken and then restored by a counterterm. More difficult problems can be studied using the same strategy such as the stability of hydrogenlike ions for any value of the proton-to-electron mass ratio M/m, the energy of the lowest spin-triplet state of helium and heliumlike ions, and the stability of the doubly excited hydrogen ion with unnatural parity. The positronium molecule, which was predicted years ago and discovered recently, can also be shown to be stable against spontaneous dissociation. Emphasis is placed on symmetry breaking, which can either spoil or improve the stability.
Introduction Helium is the natural connection between the hydrogen-like atoms (one electron outside a spherical core, such as the alkali-metal atoms of Chap. 10) and all the others in the periodic table. For these one-electron atoms the field-free description of the electron motion in terms of three quantum numbers n , ℓ , and m suffices. The other electrons are considered to form the “core” and its effect on the energy levels is reduced to the quantum defects δ ℓ , as discussed in Chap. 10. The case of helium is very different since the two ground-state electrons are in the same electronic state and differ only in the orientation of their spins. Thus spin is of paramount importance for the description of all but the hydrogenic atoms. Since helium has only two spins to deal with, their roles can be written explicitly. Because the two electrons are identical, quantum mechanics requires that the wavefunction undergoes nothing more than an unobservable phase shift when they are exchanged. This consequence is called the Pauli symmetrization principle, and is sometimes referred to as “the source of our individuality”. Moreover, it has a profound influence on the wavefunction and thus on the allowed energy states. It will be shown that this symmetry requirement dictates that two electrons cannot be in states with identical quantum numbers, and this topic will be discussed in detail in this chapter. Symmetry The profound difference between the hydrogen and helium wavefunctions arises because the two electrons are indistinguishable, and this results in a fundamental change of the energy-level structure. The concept of “spin”, introduced as a shortcut for the intrinsic magnetic moment of the electron in Chap. 7, now becomes a dominating feature of the description. Before discussing the helium energy levels, the effects of this symmetry with respect to exchange of identical particles is presented. The exchange operator In quantum mechanics, identical particles are inherently indistinguishable, so the exchange of the two electrons cannot change any observable and there should be no measurable effect on the overall wavefunction. However, there can be an overall phase change whose nature can easily be found by defining an operator P 12 that exchanges the electrons and applying it to the wavefunction. The exchange applies to all coordinates of the electron including its spin coordinate, but for simplicity only the spatial coordinate will be indicated here.
Because of considerable mathematical difficulties the Schrödinger equation can be solved exactly for only a few simple quantum systems. In particular for atoms with at least two electrons no such exact solutions exist. The most important system where an exact solution is indeed possible consists of a single electron with charge q 1 = - e in motion under the influence of a Coulomb potential about a nucleus with a positive charge q 2 = Ζe , for Ζ ≥ 1 an integer. Such a system is called a hydrogenic or hydrogen-like atom , with atomic number Z . One may view the nucleus as consisting of Ζ protons. For Ζ = 1 we obtain the hydrogen atom. For Ζ = 2, for example, the system is singly ionized helium He + ; this is helium with its two protons as usual, but stripped of one of its two electrons. Since it has only one electron but two protons it is positively charged, as indicated by the plus sign +. Similarly the lithium atom Li consists of three electrons and three protons (and four neutrons). If we strip off two electrons we obtain the ion Li ++ —doubly ionized lithium, which is the case Ζ = 3. These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.
In this review we discuss quantum phase transitions and the mapping between symmetry breaking of electronic structure configurations at the large-dimension limit and mean-field theory of phase transitions. We show that the finite size scaling method can be used for the calculations of the critical parameters of the few-body Schrodinger equation. In this approach, the finite size corresponds to the number of elements in a complete basis set used to expand the exact eigenfunction of a given Hamiltonian. The critical parameters such as the critical nuclear charges will be used to explain and predict the stability of atomic and molecular negative ions. For N-electron atoms with 2 N 86, results show that, at most, only one electron can be added to a free atom in the gas phase. However, doubly charged atomic negative ions might exist in a strong magnetic field.
Introduction I give in this chapter the quantum-mechanical description of an atom. I look in some detail at the hydrogen atom, which is the simplest atom we have, with just one proton and one electron. From the picture that emerges, we shall be able to see how to describe all other atoms. Before continuing, I need to explain what I mean when I say that the proton and electron have equal and opposite electric charges. It is because of these charges that the atom is stable, and does not spontaneously break up into the two separate particles. Electric charge and potential energy If I take a ball in my hand and then let go, it drops to the floor. This is because of the gravitational interaction between the ball and the earth. The ball had gravitational potential energy when I held it, and when I release it, this energy is progressively converted to kinetic energy as it falls. Gravitation makes two bodies move towards each other, and not away from each other: the gravitational force is always attractive. As a result of many experiments done over the years, we find that there is another kind of force in nature, somewhat analogous to, but in one aspect different from, gravitation. I take two idealized examples, and use them to show the features of this force. First I consider two electrons that I imagine to be pinned down a distance r apart.
The original intention of the author’s preoccupation with the quantum-mechanical behaviour of simple atoms and molecules such as Hydrogen and Helium was, on the one hand, the elegant simplicity of Niels Bohr’s atom model for Hydrogen, describing the metastable states of the excited electrons by planar concentric electron orbits, and, on the other hand, the hardly intelligible wave mechanical approach of Heisenberg, Schrödinger and others, describing mainly atoms with multiple electrons by three-dimensional orbitals which were characterized by probabilities of presence. Thereby the question arose whether it would be possible to find alternative atom models with well-defined electron trajectories. Therein, Louis de Broglie’s thesis of the wavy nature of electron motion implicating standing waves would have to be implemented. Nevertheless, as reviewed in the introduction, the orthodox three-dimensional concept influenced the own thinking in such a way that three-dimensional constellations for the electronic excited states were conceived. The break-through was achieved for the electronic ground state in the form of the spin-orbit coupling where the spin acts as a perpetuum mobile, inducing the orbital angular momentum h/2π. Furthermore, the insight was gained that a circularly rotating electron intrinsically corresponds to a harmonic oscillator, thus fulfilling the condition of a standing wave. Based on this concept, a double planar model was established for the H2-molecule which could be empirically verified by X-ray data from literature. However, for the two electrons containing Helium a 2D-array seemed impossible since the Pauli-principle seemed to be violated. After a long stepwise succession of 3D-attempts which turned out to be impossible—not least since eccentric forces are not possible in such a system—the here presented 2D-version for Helium was found, composed by two imaginary orthogonal electron orbits. It will enable in a subsequent publication the quantum mechanical interpretation of the thermal-radiative behaviour of Helium which was reported in the author’s publication nine years ago.