This chapter presents the origins of quantum mechanics. The story of how people hit on the highly non-intuitive world picture of quantum mechanics, in which the physical state of a system is represented by an element in an abstract linear space and its observable properties by operators in the space, is fascinating and exceedingly complicated. The much greater change from the classical world picture of Newtonian mechanics and general relativity to the quantum world picture came in many steps taken by many people, often against the better judgment of participants. There are three major elements in the story. The first is the experimental evidence that the energy of an isolated system can only assume special discrete or quantized values. The second is the idea that the energy is proportional to the frequency of a wave function associated with the system. The third is the connection between the de Broglie relation and energy quantization through the mathematical result that a wave equation with fixed boundary conditions allows only discrete quantized values of the frequency of oscillation of the wave function (as in the fundamental and harmonics of the vibration of a violin string).
This chapter presents the origins of quantum mechanics. The story of how people hit on the highly non-intuitive world picture of quantum mechanics, in which the physical state of a system is represented by an element in an abstract linear space and its observable properties by operators in the space, is fascinating and exceedingly complicated. The much greater change from the classical world picture of Newtonian mechanics and general relativity to the quantum world picture came in many steps taken by many people, often against the better judgment of participants. There are three major elements in the story. The first is the experimental evidence that the energy of an isolated system can only assume special discrete or quantized values. The second is the idea that the energy is proportional to the frequency of a wave function associated with the system. The third is the connection between the de Broglie relation and energy quantization through the mathematical result that a wave equation with fixed boundary conditions allows only discrete quantized values of the frequency of oscillation of the wave function (as in the fundamental and harmonics of the vibration of a violin string).
In the first two chapters we have examined the basic principles – superposition (p. 18), complementarity (p. 19), quantization (p. 44), statistical algorithm (p. 57), and correspondence (p. 72) (see also Subsec. 2.3.4) – and the basic entities, observables and states, of quantum mechanics, as well as the main differences with respect to classical mechanics. While what we have discussed so far is rather a static picture of observables and states, in this chapter we shall deal with quantum dynamics, i.e. with the time evolution of quantum-mechanical systems. Historically, after Bohr had provided a quantized description of the atom (see Subsec. 1.5.4), Einstein showed the quantized nature of photons (see Subsec. 1.2.1), and de Broglie hypothized the wave-like nature of matter (see Subsec. 1.5.5), the first building block of quantum mechanics was provided by the commutation relations, proposed by Heisenberg in 1925, whose consequence is represented by the uncertainty relation (see Subsec. 2.2.7 and Sec. 2.3). This was the subject of the previous chapters. The dynamical part of the theory was proposed by Schrödinger in 1926, and is known as the Schrödinger equation. It is also known as wave mechanics (see Subsec. 1.5.7). In this chapter we shall show that Heisenberg's and Schrödinger's formulations are only two different aspects of the same theory. We shall also come back to this point in Sec. 8.1.1. Here, first we shall derive the fundamental equation which rules quantum dynamics (Sec. 3.1), and, in Sec. 3.2, we shall summarize the main properties of the Schrödinger equation.
The early twentieth century was a revolutionary time in the history of physics. People often think of Einstein's special theory of relativity of 1905, which changed our conceptions of time and space. But among physicists, quantum mechanics is usually regarded as an even more radical change in our thinking about the physical world. Quantum mechanics, which was developed between 1900 and 1926, began as a theory of atoms and light but has now become the framework in terms of which all basic physical theories are expected to be cast. We need quantum ideas not only to understand atoms, molecules, and elementary particles, but also to understand the electronic properties of solids and even certain astronomical phenomena such as the stability of white dwarf stars. The theory was radical in part because it introduced probabilistic behavior as a fundamental aspect of the world, but even more because it seems to allow mutually exclusive situations to exist simultaneously in a “quantum superposition.” We will see later that the possibility of quantum superposition is largely responsible for a quantum computer's distinctive advantage over an ordinary computer. The present chapter is devoted to introducing the basic principles of quantum mechanics. There are essentially four components of the mathematical structure of quantum mechanics. We need to know how to represent (i) states, (ii) measurements, (iii) reversible transformations, and (iv) composite systems. We will develop the first three in stages, starting with a very simple case – linear polarization of photons – and working toward the most general case.
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.
Chapter 2 begins with a discussion of the de Broglie wave concept that is the foundation of quantum mechanics. The idea that particles can exhibit wave-like behavior is an important part of the explanation of why atoms have discrete energy levels and make transitions in which electromagnetic radiation is absorbed or emitted at specific frequencies. Important aspects of how quantum systems may be observed and how they develop in time are presented. The Schrödinger equation is introduced and the importance of the wavefunction covered. Mathematical simplifications that arise from considering symmetry are covered. Several examples of simple quantum systems are presented in which the calculation of electronic energy structure based on boundary conditions is illustrated. Sections on wave–particle duality and quantum observables are followed by others on the dynamics of two-level systems, mathematically complete representations of arbitrary states, and standard approaches for handling the temporal development of wavefunctions.
In this second chapter we will review the basic mathematical and physical facts about quantum mechanics and establish physical units and notation. Those readers already familiar with the subject can safely jump to the next chapter. An attempt has been made to make the presentation in this chapter as elementary as possible, and yet present the basic facts that will be needed later. There are many beautiful and important topics which will not be touched upon such as self-adjointness of Schrödinger operators, the general mathematical structure of quantum mechanics and the like. These topics are well described in other works, e.g.. Much of the following can be done in a Euclidean space of arbitrary dimension, but in this chapter the dimension of the Euclidean space is taken to be three-which is the physical case-unless otherwise stated. We do this to avoid confusion and, occasionally, complications that arise in the computation of mathematical constants. The interested reader can easily generalize what is done here to the R d , d > 3 case. Likewise, in the next chapters we mostly consider N particles, with spatial coordinates in R 3 , so that the total spatial dimension is 3 N . A Brief Review of the Connection Between Classical and Quantum Mechanics Considering the range of validity of quantum mechanics, it is not surprising that its formulation is more complicated and abstract than classical mechanics. Nevertheless, classical mechanics is a basic ingredient for quantum mechanics. One still talks about position, momentum and energy which are notions from Newtonian mechanics.
Quantum mechanics can be formulated either in terms of matrix mechanics or in terms of wave mechanics. This chapter centers on a discussion of the historical origins, mathematical structure, and extension to non-Hermitian quantum theory of matrix mechanics. The development of atomic discrete spectra and the old quantum theory showed that classical mechanics could not account for the discreteness of atomic energy levels and spectral lines, which motivated Heisenberg, Born, Jordan, and others to establish matrix mechanics centered on noncommuting physical quantities. Combining the Bohr atomic model, angular momentum quantization, and radiative transitions, one can see how matrix mechanics describes the energy level structure and quantum transitions of atomic systems, and how the Heisenberg equation of motion gives the fundamental form of quantum dynamics. The example of the harmonic oscillator further shows that the discreteness of the energy spectrum can be obtained directly from the matrix method, thereby establishing a clear connection among transition frequencies, matrix elements, and radiation-induced transitions. The matrix representation corresponds to the operator theory in Hilbert space, where state vectors, inner products, complete bases, and spectral decomposition constitute the fundamental mathematical framework of quantum mechanics. For closed quantum systems, physical observables are generally required to be represented by Hermitian or self-adjoint operators, so as to ensure that their eigenvalues possess the physically acceptable property of being real numbers. The Hermiticity of an operator is also closely related to its domain and boundary conditions, which provides a mathematical possibility for the emergence of non-Hermitian Hamiltonians. Based on these discussions, this chapter further explains how non-Hermitian dynamics is connected with open systems, dissipative processes, and special boundary conditions, thereby demonstrating the natural connection between traditional matrix mechanics and modern non-Hermitian quantum theory.