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Quantum Dynamics

Robert W. Zwanzig

Published Apr 19, 2001• 0 citations
Publisher

Abstract

Abstract For present purposes, the first thing to recall about quantum mechanics is that all dynamical quantities, instead of being functions of the location of a system in phase space as in classical mechanics, are now represented by operators in a Hilbert space of quantum states. In particular, the quantum analog of the classical phase space distribution function is the quantum mechanical density matrix. Since this is seldom discussed in introductory texts on either quantum mechanics or statistical mechanics, it may be helpful to summarize some of its basic properties.

DOI
10.1093/oso/9780195140187.003.0006

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Abstract For present purposes, the first thing to recall about quantum mechanics is that all dynamical quantities, instead of being functions of the location of a system in phase space as in classical mechanics, are now represented by operators in a Hilbert space of quantum states. In particular, the quantum analog of the classical phase space distribution function is the quantum mechanical density matrix. Since this is seldom discussed in introductory texts on either quantum mechanics or statistical mechanics, it may be helpful to summarize some of its basic properties.
The study of quantum statistical mechanics begins with a review of the basic principles of quantum mechanics. Schrödinger’s equation is introduced and Eigenstates (or stationary states) are defined. Model probability for quantum statistics is assumed to have a uniform distribution in phases. Wave functions for many-body systems are defined. The density matrix is introduced. The Planck entropy and the microcanonical ensemble are defined. The differences between classical and quantum statistical mechanics are all based on the differing concepts of a microscopic ‘state’. While the classical microscopic state (specified by a point in phase space) determines the exact position and momentum of every particle, the quantum mechanical state determines neither; quantum states can only provide probability distributions for observable quantities.
In classical mechanics the state of a system is defined by the numerical values of a set of dynamical variables such as the position coordinates and the velocities. In quantum mechanics the state of a system at an instant is represented by a unit vector in a Hilbert space, where a set of axes are the eigenvectors of a complete set of observables. The description of quantum dynamics where the wave function is time-dependent and the operators describing the observables are time-independent is known as the Schrodinger picture. The use of total time derivative of operator that depends on the time evolution of the wave function as well as on any intrinsic time-dependence in the operators simplifies the development of quantum mechanics and allows the development to more closely follow the corresponding development of classical mechanics. The difference between the Schrodinger and Heisenberg pictures is best understood as the difference in the basic set of observables.
Our purpose in this chapter is to present the key concepts of quantum mechanics in the language of Hilbert spaces. The reader who has not previously met the physical ideas motivating quantum mechanics, and some of the more elementary applications of Schrödinger's equation, is encouraged to read any of a number of excellent texts on the subject such as [1–4]. Otherwise, the statements given here must to a large extent be taken on trust – not an altogether easy thing to do, since the basic assertions of quantum theory are frequently counterintuitive to anyone steeped in the classical view of physics. Quantum mechanics is frequently presented in the form of several postulates, as though it were an axiomatic system such as Euclidean geometry. As often presented, these postulates may not meet the standards of mathematical rigour required for a strictly logical set of axioms, so that little is gained by such an approach. We will do things a little more informally here. For those only interested in the mathematical aspects of quantum mechanics and the role of Hilbert space see [5–8]. Many of the standard applications, such as the hydrogen atom, will be omitted here as they can be found in all standard textbooks, and we leave aside the enormous topic of measurement theory and interpretations of quantum mechanics. This is not to say that we need be totally comfortable with quantum theory as it stands. Undoubtedly, there are some philosophically disquieting features in the theory, often expressed in the form of socalled paradoxes.
In contrast to classical physics, the language of quantum mechanics involves operators and wave functions (or, more generally, density operators). However, in 1932, Wigner formulated quantum mechanics in terms of a distribution function W(q,p)W(q,p)W(q,p), the marginals of which yield the correct quantum probabilities for qqq and ppp separately \cite{wigner}. Its usefulness stems from the fact that it provides a re-expression of quantum mechanics in terms of classical concepts so that quantum mechanical expectation values are now expressed as averages over phase-space distribution functions. In other words, statistical information is transferred from the density operator to a quasi-classical (distribution) function.
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.