In the 1920s, the old quantum theory was gradually being superseded by the new quantum theory. The cornerstone of the old theory was Bohr’s model of the hydrogen atom, which predicted that an electron cannot orbit the proton in the hydrogen atom in any arbitrary fashion. Orbits are “quantized,” meaning that only certain sizes, shapes, and magnetic properties are allowed. The principal quantum number n determined the allowed radii of the orbits, the orbital quantum number l determined the allowed shapes, and the magnetic quantum number m determined the magnetic behavior. Additionally, there is a fourth quantum number s which denotes the fact that the electron has an additional angular momentum, loosely associated with self rotation about its own axis, and that is quantized in units of (1/2)~. The old quantum theory was useful to infer the existence of discrete energy levels in atoms, calculate energy spacings between these levels, and therefore allowed one to interpret atomic spectra. The new quantum theory appeared to be more revolutionary and more powerful. It was triggered by Heisenberg’s discovery of matrix mechanics and Schro¨dinger’s discovery of wave mechanics. These two formalisms would not only predict the quantization of energy and provide a prescription to determine the energy difference between the levels (and thus explain the multiplicity of atomic spectra), but also allow one to calculate easily probabilities of transitions between different quantized energy states. At first, matrix mechanics and wave mechanics looked entirely different in their mathematical appearance and physical meaning. However, Schro¨dinger and Eckart [1] independently showed that the two theories are mathematically equivalent. Toward the end of 1926, Dirac unified the two theories using the concept of state vector and thus established the transformation theory of quantum mechanics. This ultimately had a profound implication for the quantum mechanical (mathematical) recipe to treat spin, as we will show in this chapter. The transformation theory is the mathematical recipe to handle modern quantum mechanics. In Heisenberg’s matrix mechanics, a physical quantity is expressed by a matrix, whereas in Schro¨dinger’s wave mechanics, a physical quantity is expressed by a linear operator. In the unified transformation theory, physical quantities are represented by abstract linear operators called Dirac’s q-numbers, which are linear operators in an infinite-dimensional linear space. Depending upon which types of orthogonal coordinate systems are used in this linear space, either matrix mechanics or wave mechanics emerges.
In the 1920s, the old quantum theory was gradually being superseded by the new quantum theory. The cornerstone of the old theory was Bohr’s model of the hydrogen atom, which predicted that an electron cannot orbit the proton in the hydrogen atom in any arbitrary fashion. Orbits are “quantized,” meaning that only certain sizes, shapes, and magnetic properties are allowed. The principal quantum number n determined the allowed radii of the orbits, the orbital quantum number l determined the allowed shapes, and the magnetic quantum number m determined the magnetic behavior. Additionally, there is a fourth quantum number s which denotes the fact that the electron has an additional angular momentum, loosely associated with self rotation about its own axis, and that is quantized in units of (1/2)~. The old quantum theory was useful to infer the existence of discrete energy levels in atoms, calculate energy spacings between these levels, and therefore allowed one to interpret atomic spectra. The new quantum theory appeared to be more revolutionary and more powerful. It was triggered by Heisenberg’s discovery of matrix mechanics and Schro¨dinger’s discovery of wave mechanics. These two formalisms would not only predict the quantization of energy and provide a prescription to determine the energy difference between the levels (and thus explain the multiplicity of atomic spectra), but also allow one to calculate easily probabilities of transitions between different quantized energy states. At first, matrix mechanics and wave mechanics looked entirely different in their mathematical appearance and physical meaning. However, Schro¨dinger and Eckart [1] independently showed that the two theories are mathematically equivalent. Toward the end of 1926, Dirac unified the two theories using the concept of state vector and thus established the transformation theory of quantum mechanics. This ultimately had a profound implication for the quantum mechanical (mathematical) recipe to treat spin, as we will show in this chapter. The transformation theory is the mathematical recipe to handle modern quantum mechanics. In Heisenberg’s matrix mechanics, a physical quantity is expressed by a matrix, whereas in Schro¨dinger’s wave mechanics, a physical quantity is expressed by a linear operator. In the unified transformation theory, physical quantities are represented by abstract linear operators called Dirac’s q-numbers, which are linear operators in an infinite-dimensional linear space. Depending upon which types of orthogonal coordinate systems are used in this linear space, either matrix mechanics or wave mechanics emerges.
In the 1920s, the old quantum theory was gradually being superseded by the new quantum theory. The cornerstone of the old theory was Bohr’s model of the hydrogen atom which predicted that an electron cannot orbit the proton in the hydrogen atom in any arbitrary fashion. Orbits are “quantized”, meaning that only certain sizes, shapes and magnetic properties are allowed. The principal quantum number n determined the allowed radii of the orbits, the orbital quantum number l determined the allowed shapes, and the magnetic quantum number m determined the magnetic behavior. Additionally, there is a fourth quantum number s which denotes the fact that the electron has an additional angular momentum, loosely associated with self rotation about its own axis, and that is quantized in units of (1/2). The old quantum theory was useful to infer the existence of discrete energy levels in atoms, calculate energy spacings between these levels, and therefore allowed one to interpret atomic spectra.
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.
First, the experimental foundations for the existence of a new dynamical variable, the spin of particles, are presented. The Pauli equation is then derived in detail, two applications are given and the energy levels of a particle with spin in a constant magnetic field are studied. This is the analysis of Landau levels, which can be performed by using the known results on the spectrum of harmonic oscillators. In this chapter we also study in detail the addition of orbital angular momentum and spin, as well as the spin–orbit interaction with the resulting Thomas precession. Stern-Gerlach experiment and electron spin The hypothesis that the electron has an intrinsic magnetic moment and an angular momentum, in short a spin , was first suggested in Uhlenbeck and Goudsmit (1926). They noticed, even before the discovery of quantum mechanics, that a complete description of spectra was not possible unless a magnetic moment and a mechanical moment were ascribed to the electron, and hence the concept of an electron as a point charge was insufficient. First, let us therefore try to understand how a magnetic moment can be associated to an atomic system. For this purpose, consider for simplicity the Bohr model of an hydrogen atom, where the electron moves along a circular orbit and rotates with orbital angular momentum L .
Chapter 4 deals with Quantum Mechanical (QM) phenomena. The first section describes the first attempts at quantization of energy, momentum, angular momentum, etc. We start with Plank's solution to the black-body problem, introducing the concept of photons: discrete packets of electromagnetic energy. We show how Plank's description of black-body radiation is perfectly fit by the cosmic microwave radiation, providing the strongest evidence for the Big-Bang at the origin of the Universe. We then describe Bohr's solution to the paradoxical stability of atoms, introducing quantization of angular momentum (or action) and correctly predicting the energy levels of the hydrogen atom. We show how Einstein used Plank's idea to explain the photo-electric effect (an effect exploited in CCD cameras and solar cells) and how he used Bohr's understanding of energy levels in atoms to provide an intuitive explanation of Plank's law. Einstein insight opened the way to the field of spectroscopy and the development of the laser. In the second section, following the lead of Dirac, we show that QM is equivalent to Linear Algebra in the space of complex functions (which describe the state of the system). We show that Schrödinger's equation is a natural consequence of that description, once the relation between energy and frequency established by Plank (for photons) and de Broglie (for particles) is taken into account. In the context of the chiral ammonia molecule we discuss the queerness of QM which describes physical systems as superposition of states (such as left and right chirality state of a molecule, dead and alive cat). We show that this queerness is nonetheless supported by experiments and is behind much of our technology: masers and lasers, atomic clocks, semiconductors (diodes, transistors, etc.). In the following section we introduce the representation of operators in QM (the equivalent of matrices in linear algebra): momentum, position, energy, etc. which correspond to measurements on the system. We show that the non-commutability of some operators (common with matrix operations) leads to Heisenberg uncertainty principle: the position and momentum of a particle cannot be determined with absolute precision. We discuss the solution of Schrödinger's equation for free particles demonstrating their equivalence with EM phenomena: particles undergo refraction and diffraction, exemplifying the particle/wave duality inherent to QM systems. We discuss QM tunneling and its use in the Scanning Tunneling Microscope. In the following section we study Dirac's equation: the successful attempt by Dirac to unify QM with Einstein's relativity, with the resulting prediction of anti-particles and spin. We then solve for the energy levels of electrons in the hydrogen atom (from Schrödinger's equation) and show that the existence of spin profoundly affects the behavior of electrons in an atom: they cannot share the same energy level, a rule known as Pauli's exclusion principle. Pauli's principle is central to the understanding of the chemical properties of atoms and fully explains Mendeleev's periodic table of the elements. In the next section we discuss along with two exactly soluble systems (diatomic rotational and vibrational levels), various approximations used to study systems (e.g. molecules) for which there are no analytical solutions. In particular, we introduce Pauling's variational approach, Hückel molecular orbital theory and time independent perturbation theory. We apply those approaches to determine the energy levels in alkenes, in multi-electron atoms and in systems under constant electric or magnetic field (such as in Magnetic Resonance Imaging). In the last section we discuss time dependent perturbation theory. We use it to establish the rules allowing for transitions between energy levels and revisit Einstein description of absorption/emission phenomena.
The mechanical angular momentum and magnetic moment of the electron and proton spin have been calculated semiclassically with the aid of the uncertainty principle for energy and time.The spin effects of both kinds of the elementary particles can be expressed in terms of similar formulae.The quantization of the spin motion has been done on the basis of the old quantum theory.It gives a quantum number n = 1/2 as the index of the spin state acceptable for both the electron and proton particle.In effect of the spin existence the electron motion in the hydrogen atom can be represented as a drift motion accomplished in a combined electric and magnetic field.More than 18,000 spin oscillations accompany one drift circulation performed along the lowest orbit of the Bohr atom.The semiclassical theory developed in the paper has been applied to calculate the doublet separation of the experimentally well-examined D line entering the spectrum of the sodium atom.This separation is found to be much similar to that obtained according to the relativistic old quantum theory.