Abstract Section I.—The exclusion principle of Pauli was introduced into the old quantum theory as an empirical fact that had been brought to light in the ordering of spectra. The new mechanics has provided some sort of explanation of the principle, for in a closed system with many electrons the mathematically possible stationary states can be separated into a number of groups, with the property that transitions between stationary states in different groups cannot occur. One of these group is made up of the stationary states corresponding occur. One of the these groups is made up of the stationary states corresponding to wave functions that are antisymmetrical in the co-ordinates of the electrons. Apart from accidental degeneracies, the stationary states in different groups have different energy values. The exclusion principle then states that only energy values belonging to the antisymmertical group are found in nature. The exclusion principle has had great success not only in explaining the spectra of helium and of more complicated atoms, but also, under the form of the Fermi-Dirac statistics, in accounting for metallic conduction and ferromagnetism. In all these phenomena we are dealing with systems is stationary states, possessing energy values which are discrete, although they may lie very close together. Now, as was first emphasised by Oppenheimer, we must also use antisymmetrical wave-functions to describe aperiodic phenomena, such as the collision between an electron and an atom. If we do not, we obtain probabilities for the formation of atoms whose wave-funtions are not antisymmetrical, as we shall show in section 4, where we consider the collision between an electron and a helium atom. A helium atom described by a symmetrical wave-function would show a singlet series in palce of the observed triplets and triplet series in place of the observed singlets. The wave-functions of open systems are essentially degenerate; the symmetical and antisymmetrical solution are not separated from one another by a finite energy difference; but for any arbitrary value of the energy (and of the other integrals of the motion) we can form a symmetrical and an antisymmetrical solution. This is somewhat fundamental difference between open and closed systems. For closed systems containing two electrons there exist only the symmetrical and the antisymmetical solution; but for open systems we might take any combination of the two. In fact, to describe an observable phenomenon such as a collision, the wave-function that it would first occur to us to use is a combination of the two. To fix our ideas we shall discuss the collision between two electrons. Our arguments could equally well be applied to the collision between an electron and a hydrogen atom, the problem originally discussed by Born; but the former is the simpler case, and perhaps illustrates our theory better.
Abstract Section I.—The exclusion principle of Pauli was introduced into the old quantum theory as an empirical fact that had been brought to light in the ordering of spectra. The new mechanics has provided some sort of explanation of the principle, for in a closed system with many electrons the mathematically possible stationary states can be separated into a number of groups, with the property that transitions between stationary states in different groups cannot occur. One of these group is made up of the stationary states corresponding occur. One of the these groups is made up of the stationary states corresponding to wave functions that are antisymmetrical in the co-ordinates of the electrons. Apart from accidental degeneracies, the stationary states in different groups have different energy values. The exclusion principle then states that only energy values belonging to the antisymmertical group are found in nature. The exclusion principle has had great success not only in explaining the spectra of helium and of more complicated atoms, but also, under the form of the Fermi-Dirac statistics, in accounting for metallic conduction and ferromagnetism. In all these phenomena we are dealing with systems is stationary states, possessing energy values which are discrete, although they may lie very close together. Now, as was first emphasised by Oppenheimer, we must also use antisymmetrical wave-functions to describe aperiodic phenomena, such as the collision between an electron and an atom. If we do not, we obtain probabilities for the formation of atoms whose wave-funtions are not antisymmetrical, as we shall show in section 4, where we consider the collision between an electron and a helium atom. A helium atom described by a symmetrical wave-function would show a singlet series in palce of the observed triplets and triplet series in place of the observed singlets. The wave-functions of open systems are essentially degenerate; the symmetical and antisymmetrical solution are not separated from one another by a finite energy difference; but for any arbitrary value of the energy (and of the other integrals of the motion) we can form a symmetrical and an antisymmetrical solution. This is somewhat fundamental difference between open and closed systems. For closed systems containing two electrons there exist only the symmetrical and the antisymmetical solution; but for open systems we might take any combination of the two. In fact, to describe an observable phenomenon such as a collision, the wave-function that it would first occur to us to use is a combination of the two. To fix our ideas we shall discuss the collision between two electrons. Our arguments could equally well be applied to the collision between an electron and a hydrogen atom, the problem originally discussed by Born; but the former is the simpler case, and perhaps illustrates our theory better.
The modern state of the Pauli Exclusion Principle (PEP) is discussed. PEP can be considered from two viewpoints. On the one hand, it asserts that particles with half-integer spin (fermions) are described by antisymmetric wave functions, and particles with integer spin (bosons) are described by symmetric wave functions. This is the so-called spin-statistics connection (SSC). As we will discuss, the physical reasons why SSC exists are still unknown. On the other hand, according to PEP, the permutation symmetry of the total wave functions can be only of two types: symmetric or antisymmetric, both belong to one-dimensional representations of the permutation group, all other types of permutation symmetry are forbidden; whereas the solution of the Schrödinger equation may have any permutation symmetry. It is demonstrated that the proof in some widespread textbooks on quantum mechanics that only symmetric and antisymmetric states (one-dimensional representations of the permutation group) can exist is wrong. However, the scenarios, in which an arbitrary permutation symmetry (degenerate permutation states) is permitted lead to contradictions with the concepts of particle identity and their independence. Thus, the existence in our nature particles only in nondegenerate permutation states (symmetric and antisymmetric) is not accidental and so-called symmetrization postulate may not be considered as a postulate, since all other symmetry options for the total wave function may not be realized. From this an important conclusion follows: we may not expect that in future some unknown elementary particles can be discovered that are not fermions or bosons.
Abstract One of the outstanding differences between classical theory and quantum mechanics is the importance which the latter attaches to the identity of particles. Although perfectly well realised before the introduction of modern quantum theory, the fact that two electrons are experimentally indistinguishable did not introduce any novel features into the dynamics of many electron systems on Bohr’s theory. However, Heisenberg showed that these identity relations are of fundamental importance in many body problems, and was able to explain the formerly very puzzling characteristic of the spectrum of neutral helium, its division into two non-combining term systems. Owing to the identity of the particles, the wave function representing such a system must have certain symmetry properties; for the particles known in Nature this symmetry characteristic is that the function be either symmetric or anti-symmetric in the co-ordinates of the particles. For particles with a spin such as the electron and proton, only antisymmetry is allowed (Pauli’s principle), while for α-particles the wave function must be symmetrical. Since Heisenberg’s explanation of the helium spectrum the theory of anti-symmetric electron wave functions has been extended to describe the general features of the spectra of all atoms, while it appears from the work of Heitler and London that the theory is of fundamental importance in the explanation of chemical combination between atoms. Again, in furnishing a new statistics it is an essential feature of the theory of metals. As the effect of the identity relations depends on the fact that exchanging the electrons does not alter the system in any way, these effects are known as exchange phenomena.
Abstract It is well-known that the problem of the collision between two particles interacting according to the inverse square law is exactly soluble on the wave mechanics, and that the solution yields the same scattering laws as the classical theory. If, however, the two particles are identical, e.g., two electrons or two α-particles, this is not necessarily the case; for the wave functions used must be antisymmetrical or symmetrical in the co-ordinates of the two particles; and this may affect the scattering laws. In this paper we shall discuss the collision between two particles possessing spin, such as electrons, and also between two particles without spin, such as α-particles. Assuming an inverse square law force between the particles, and neglecting the actual spin forces, we shall deduce from the symmetry properties of the wave functions a scattering law differing considerably from the classical. We shall also mention the various methods by which the effect could be observed, and give some experimental evidence in its favour. The application of the exclusion principle to collision problems has been discussed by the author in a previous paper. Suppose we wish to describe the motion of two particles interacting in any field of force. We obtain a solution w(r1 r2) of the wave equation, where r1 refers to the position of the first particle, and r2 to that of the second. If we did not use antisymmetrical wave functions, we should argue that the probability that the first particle should be at r1 and the second at r 2 would be |w (r1 r2)|2, and therefore the probability that one particle should be at r1 and the other at r2 would be |w (r1 r2)|2 + |w(r2 r1)|
The Pauli exclusion principle (PEP) can be considered from two aspects. First, it asserts that particles that have half-integer spin (fermions) are described by antisymmetric wave functions, and particles that have integer spin (bosons) are described by symmetric wave functions. It is called spin-statistics connection (SSC). The physical reasons why SSC exists are still unknown. On the other hand, PEP is not reduced to SSC and can be consider from another aspect, according to it, the permutation symmetry of the total wave function can be only of two types: symmetric or antisymmetric. They both belong to one-dimensional representations of the permutation group, while other types of permutation symmetry are forbidden. However, the solution of the Schrödinger equation may have any permutation symmetry. We analyze this second aspect of PEP and demonstrate that proofs of PEP in some wide-spread textbooks on quantum mechanics, basing on the indistinguishability principle, are incorrect. The indistinguishability principle is insensitive to the permutation symmetry of wave function. So, it cannot be used as a criterion for the PEP verification. However, as follows from our analysis of possible scenarios, the permission of states with permutation symmetry more general than symmetric and antisymmetric leads to contradictions with the concepts of particle identity and their independence. Thus, the existence in our Nature particles only in symmetric and antisymmetric permutation states is not accidental, since all symmetry options for the total wave function, except the antisymmetric and symmetric, cannot be realized. From this an important conclusion follows, we may not expect that in future some unknown elementary particles that are not fermions or bosons can be discovered.
This chapter assesses some applications drawn from atomic and molecular structure. It deals with the structures of the lighter atoms and the simplest molecule, molecular hydrogen. The main approximation method used here is the energy variational principle, which is a powerful technique for computing the low-lying energies of a system such as an atom or molecule. The chapter then introduces the Pauli exclusion principle, which governs the symmetry of the state vector for a system of identical particles such as electrons. Two general features of the exclusion principle are worth noting. First, although the spins make only a very weak contribution to the Hamiltonians for helium, the lowest energy state with spin one is above the spin zero ground state, which is a considerable difference. Second, an electron arriving as a cosmic ray particle from a distant galaxy has to have a wave function antisymmetric with respect to the local electrons, even though the new electron has been away from us for a long time.
In classical physics it was assumed that a system of two bodies, both having the same mechanical and electrical properties, would show the same behavior regardless of their complete identity. This assumption, that gave rise to the paradoxes of Gibbs and of Einstein which are here discussed, must be abandoned in atomic physics. We must distinguish sharply between identical particles and those that are only quasiidentical, in the sense that they are the same in mass, charge and the potential fields to which they give rise. All of the results which have hitherto been obtained in quantum mechanics are valid even if we assume that two particles such as two electrons or two helium nuclei are only quasi-identical. The postulate of complete identity is a new mathematical condition which, operating simultaneously with the wave equation and its boundary conditions, restricts the number of possible solutions of the equation and thus gives rise mathematically to a number of exclusion laws such as those which have been empirically obtained.The assumption of identity is equivalent to the mathematical assumption that the ordinary configuration space is degenerate, in the sense that one portion is a mere reflection of another. By this method it is shown that if the wave function is a scalar, the laws of exclusion are obtained without ambiguity. Thus a perfectly symmetrical diatomic gas in its simplest electronic state can have only even rotational levels. It is pointed out that the experimental results with O2(O16O16) and He2 show that these atoms exist in a single nuclear state. It is predicted that with heavier atoms both even and odd states will be found owing to the existence of isobars. The monatomic gas is then discussed and it is shown that, if the Schr\"odinger function is a scalar, only the Bose-Einstein statistics are possible.The phenomenon of spin introduces a vector character into the wave function. If we assume that the spin factor changes sign upon reflection when the number of units of spin is odd but not when the number of units of spin is even, we have all the cases of exclusion now known, including the case of the nitrogen molecule. As an example of the method, the problem of the helium atom is discussed.