Wave mechanics In the classical dynamics the state of the system whose coordinates are q 1 … q s and momenta p 1 … p s is denoted by a point in 2s-dimensional space (the q-space); changes in the system are indicated by the passage of the point along some curve in this space, a ‘ray,’ it may be called. Schrödinger's new concept is that changes in the system should be represented in the q-space not by ‘rays’ but by ‘waves.’ He regards the classical mechanics as only an approximation to actual mechanical events, which he says can only be described by wave mechanics; the former in his view bears to the latter just the same relation as geometrical (or ‘ray’) optics does to physical (or ‘wave’) optics. A large scale (macroscopic) mechanical process corresponds to a wave signal in the g-space, which can be regarded as a point in comparison with the geometrical structure of its path. But for small scale (microscopic) processes, such as atomic phenomena are, the rigorous wave theory must be used. The wave equation must replace the usual dynamical equations. The latter are just as unfruitful for the purposes of atom mechanics as geometrical optics alone would be to clear up the fine points of diffraction phenomena.
Wave mechanics In the classical dynamics the state of the system whose coordinates are q 1 … q s and momenta p 1 … p s is denoted by a point in 2s-dimensional space (the q-space); changes in the system are indicated by the passage of the point along some curve in this space, a ‘ray,’ it may be called. Schrödinger's new concept is that changes in the system should be represented in the q-space not by ‘rays’ but by ‘waves.’ He regards the classical mechanics as only an approximation to actual mechanical events, which he says can only be described by wave mechanics; the former in his view bears to the latter just the same relation as geometrical (or ‘ray’) optics does to physical (or ‘wave’) optics. A large scale (macroscopic) mechanical process corresponds to a wave signal in the g-space, which can be regarded as a point in comparison with the geometrical structure of its path. But for small scale (microscopic) processes, such as atomic phenomena are, the rigorous wave theory must be used. The wave equation must replace the usual dynamical equations. The latter are just as unfruitful for the purposes of atom mechanics as geometrical optics alone would be to clear up the fine points of diffraction phenomena.
According to Schrödinger's ideas, classical dynamics of point particles should correspond to the « geometrical optics » limit of a linear wave equation, in just the same way as ray optics is the limit of wave optics. It is shown that the « geometrical optics » analogy leads to the correspondence between a classical Hamiltonian H and a linear wave equation in a natural and general way. In particular, the correspondence is unambiguous also in the case where H contains mixed terms involving momentum and position. This is obtained through a theory of the dispersion relations, which leads to properly define the group velocity and to enlighten its role. Using this latter notion, it is shown that, for a quite general class of potentials, « momentum states » can be defined in a physically more satisfying way than by assuming plane waves. These momentum states are solutions of the time-dependent Schrödinger equation and their amplitude functions move rigidly on a well-defined trajectory. In the case of a spatially uniform force field, such momentum states must have a singularity and the trajectory is defined by Newton's second law in the given force field.
Classical mechanics, which gives a fairly accurate description of large systems (e.g., solar system) as also of mechanical systems in our every day life, however, breaks down when applied to small (microscopic) systems such as molecules, atoms and nuclei. For example, (1) classical mechanics cannot even explain why the atoms are stable at all. A classical atom with electrons moving in circular or elliptic orbits around the nucleus would continuously radiate energy in the form of electromagnetic radiation because an accelerated charge does radiate energy. As a result the radius of the orbit would become smaller and smaller, resulting in instability of the atom. On the other hand, the atoms are found to be remarkably stable in practice. (2) Another fact of observation that classical mechanics fails to explain is wave particle duality in radiation as well as in material particles. It is well known that light exhibits the phenomena of interference, diffraction and polarization which can be easily understood on the basis of wave aspect of radiation. But light also exhibits the phenomena of photo-electric effect, Compton effect and Raman effect which can only be understood in terms of corpuscular or quantum aspect of radiation. The dual behavior of light, or radiation cannot be consistently understood on the basis of classical concepts alone or explained away by saying that light behaves as wave or particle depending on the kind of experiment we do with it (complementarity). Moreover, a beam of material particles, like electrons and neutrons, demonstrates wave-like properties (e.g., diffraction). A brief outline of phenomena that require quantum mechanics for their understanding follows.
Let us return from optics to mechanics and explore the analogy to its fullest extent. In optics the old system of mechanics corresponds to intellectually operating with isolated mutually independent light rays. The new undulatory mechanics corresponds to the wave theory of light . Erwin Schrödinger, Nobel lecture , 1933 In this chapter we shall see that electromagnetic waves and electrons feature a number of common properties under conditions of spatial confinement. Simple and familiar problems from introductory quantum mechanics and textbook wave optics are recalled in this chapter to emphasize the basic features of waves in spatially inhomogeneous media. Herewith we make a first step towards understanding the properties of electrons and electromagnetic waves in nanostructures and notice that these properties in many instances are counterparts. Different formulas and statements of this chapter can be found in handbooks on quantum mechanics and wave optics. A few textbooks on quantum mechanics do consider analogies of propagation and reflection phenomena in wave optics with those in wave mechanics. Isomorphism of the Schrödinger and Helmholtz equations In Chapter 2 we discussed that an electron in quantum mechanics is described by the wave function, the square of its absolute value giving the probability of finding an electron at a specific point in space. This function satisfies the Schrödinger equation (2.56) which is the second-order differential equation with respect to space and the first-order differential equation with respect to time.
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.
Classical mechanics is usually valid at the macro scale. The changes in the position and the momentum of the object over time are described by the Hamiltonian equation of motion. The wave function in quantum mechanics, if unobserved, evolves in a smooth and continuous way according to the Schrodinger equation, which is related to the Hamiltonian equation of motion. This equation describes a linear superposition of different states at time. A quantum mechanical description of a physical system is related to a probabilistic representation; it is described by a vector in Hilbert space. This description extends the two- or three-dimensional Euclidean space into spaces that have any finite or infinite number of dimensions. The state of a compound system is projected to the subspace that corresponds to the observed state and the vector representing the state is renormalized to the unit length. An observable describes a subspace for some dimensions with a special case of one dimension.
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.