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International Journal of Quantum Chemistry

On the conditions for physical admissibility of Schrödinger wave functions

Hui-yun Pan, Zhao Zu Sen

Published Nov 1, 1991• 4 citations
Publisher

Abstract

Abstract It is shown that the dispute about the conditions for physical admissibility of Schrödinger wave functions may be settled if the following two questions are clarified: (a) Are these condittions rooted in the foundations of quantum mechanics or invoked only for particular physical models? (b) Do we consider either the position‐space wave function or the momentum‐space wave function? Both the case of closed states and scattering states are considered. Some general remarks about these conditions are made in the Conclusion.

DOI
10.1002/qua.560400504

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Abstract It is shown that the dispute about the conditions for physical admissibility of Schrödinger wave functions may be settled if the following two questions are clarified: (a) Are these condittions rooted in the foundations of quantum mechanics or invoked only for particular physical models? (b) Do we consider either the position‐space wave function or the momentum‐space wave function? Both the case of closed states and scattering states are considered. Some general remarks about these conditions are made in the Conclusion.
Admissibility conditions for wave functions are derived from general quantum-mechanical principles. The conditions apply in general curvilinear coordinates to functions that describe general N-particle systems. They restrict the behavior of wave functions so severely as to suggest that the Hilbert space of ordinary quantum mechanics cannot be enlarged unless the fundamental principles of quantum mechanics are modified. One of the conditions implies that all particles must be either fermions or bosons, i.e., that no particles obeying intermediate statistics can exist.
We have seen in the previous chapter how useful wave mechanics can be in solving physical problems. But wave mechanics has several limitations. It describes physical states by means of wave functions, which are functions of the positions of the particles of the system, but why should we single out position as the fundamental physical observable? For instance, we might want to describe states in terms of probability amplitudes for particles to have certain values of the momentum or energy rather than the position. A more fundamental limitation: There are attributes of physical systems that cannot be described at all in terms of the positions and momenta of a set of particles. One of these attributes is spin , which will be the subject of Chapter 4. Another is the value of the electric or magnetic field at some point in space, treated in Chapter 11. This chapter will describe the principles of quantum mechanics in a formalism which is essentially the “transformation theory” of Dirac, mentioned briefly in Section 1.4. This formalism generalizes both the wave mechanics of Schrödinger and the matrix mechanics of Heisenberg, and is sufficiently comprehensive to apply to any sort of physical system. States The first postulate of quantum mechanics is that physical states can be represented as vectors in a sort of abstract space known as Hilbert space . Before getting into Hilbert space, I need to say a bit about vectors in general. In kindergarten we learn that vectors are quantities with both magnitude and direction. Later, when we study analytic geometry, we learn instead to describe a vector in d dimensions as a string of d numbers, the components of the vector. This latter approach lends itself well to calculation, but in some respects the kindergarten version is better, because it allows us to describe relations among vectors without specifying a coordinate system. For instance, a statement that one vector is parallel to a second vector, or perpendicular to a third, has nothing to do with how we choose our coordinate system.
We have seen in the previous chapter how useful wave mechanics can be in solving physical problems. But wave mechanics has several limitations. It describes physical states by means of wave functions, which are functions of the positions of the particles of the system, but why should we single out position as the fundamental physical observable? For instance, we might want to describe states in terms of probability amplitudes for particles to have certain values of the momentum or energy rather than the position. A more fundamental limitation is that there are attributes of physical systems that cannot be described at all in terms of the positions and momenta of a set of particles. One of these attributes is spin , which will be a chief subject of Chapter 4. Another is the value of the electric or magnetic field at some point in space, treated in Chapter 11. This chapter will describe the principles of quantum mechanics in a formalism which is essentially the “transformation theory” of Dirac, mentioned briefly in Section 1.4. This formalism generalizes both the wave mechanics of Schrödinger and the matrix mechanics of Heisenberg, and is sufficiently comprehensive to apply to any sort of physical system. States The first postulate of quantum mechanics is that physical states can be represented as vectors in a sort of abstract space known as Hilbert space . Before getting into Hilbert space, I need to say a bit about vectors in general. In kindergarten we learn that vectors are quantities with both magnitude and direction. Later, when we study analytic geometry, we learn instead to describe a vector in d dimensions as a string of d numbers, the components of the vector. The latter approach lends itself well to calculation, but in some respects the kindergarten version is better, because it allows us to describe relations among vectors without specifying a coordinate system. For instance, a statement that one vector is parallel to a second vector, or perpendicular to a third, has nothing to do with how we choose our coordinate system. Here we will formulate what we mean by vector spaces in general, and Hilbert space in particular, in a way that is independent of the coordinates we use to describe directions in these spaces.
The nature of quantum description is clarified. It is shown that complex-valued probability amplitudes are admissible within classical Hamiltonian mechanics. According to standard probability theory, such a description is always possible. The case of a spherical phase space is considered. It is shown that, in such a classical theory, there appears a universal constant that has dimensions of action ( h ), as well as Fock space and all attributes of quantum mechanics. Excitations of a chain of such systems are described by the equations of quantum mechanics with a correct normalization condition. It is shown that an answer to the question of what a particle and its wave function are is provided by quantum field theory (these are a single-particle field excitation and a function that describes it). Experiments are proposed that would make it possible to solve the problem of the physical nature of the wave function.