Abstract Chapter 10 introduces the concept of quantum ensembles and their descrption via the ensemble density matrix. The chapter begins by setting up the quantum manybody problem and demonstrating the difficulty in solving the time-independent Schrödinger equation for the energy eigenvalues of a manybody Hamiltonian. This naturally leads to the concept of quantum ensembles and their formulation in terms of the density matrix. Eigenvalues of the density matrx are shown to represent probabilities associated with the quantum states that constitute the ensemble. The time-dependence of the density matrix is shown to be determined by the quantum Liouville equation. The quantum Liouville equation is solved under equilibrium conditions, and the solutions are shown to commute with the Hamiltonian. Thus, the eigenvalues of the solution are shown give the probabilities associated with different energy levels. Quantum partition functions in different ensembles are derived from these eigenvalues. Finally, the quantum analog of entropy maximization is used to derive the quantum canonical ensemble.
Abstract Chapter 10 introduces the concept of quantum ensembles and their descrption via the ensemble density matrix. The chapter begins by setting up the quantum manybody problem and demonstrating the difficulty in solving the time-independent Schrödinger equation for the energy eigenvalues of a manybody Hamiltonian. This naturally leads to the concept of quantum ensembles and their formulation in terms of the density matrix. Eigenvalues of the density matrx are shown to represent probabilities associated with the quantum states that constitute the ensemble. The time-dependence of the density matrix is shown to be determined by the quantum Liouville equation. The quantum Liouville equation is solved under equilibrium conditions, and the solutions are shown to commute with the Hamiltonian. Thus, the eigenvalues of the solution are shown give the probabilities associated with different energy levels. Quantum partition functions in different ensembles are derived from these eigenvalues. Finally, the quantum analog of entropy maximization is used to derive the quantum canonical ensemble.
In many cases, measurements are performed on “mixed” ensembles of realizations of a system, which cannot be associated with a single vector in its Hilbert space. In these cases the state of the system is represented by a proper “density operator.” It is instructive to associate density operators with state vectors in a vector space, termed Liouville’s space, where the Schrödinger equation is reformulated as the Liouville–Von Neumann equation. An important consequence of this equation is that the density operator of a system at equilibrium must commute with its Hamiltonian. Namely, the matrix representation of the density operator in the basis of Hamiltonian eigenstates is diagonal, where the diagonal elements are the relative populations of the system’s Hamiltonian eigenstates. The equilibrium populations are revealed by maximizing the (Von Neumann) entropy, subject to given constraints. We derive the equilibrium density operator explicitly for the cases of canonical and grand canonical ensembles.
Abstract Chapter 14 covers the statistical mechanics of driven quantum systems and the non-equilibrium ensembles associated with them. The topic is presented both from the state-vector and density matrix perspectives. The chapter begins with a discussion of driving forces resulting from light-matter interactions and their treatment via time-dependent perturbation theory. The Fermi Golden Rule is derived, and it is shown how to incorporate the Golden Rule into the calculation of frequency spectra within the canonical ensemble, which then connects to canonical quantum time correlation functions. The formalism is derived again from the quantum Liouville equation. The discussion then turns to the challenge of computing quantum time correlation functions and approximate techniques based on the Feynman path integral of Chapter 12. These schemes include centroid and ring-polymer molecular dynamics as well as open-path integral methods
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.
A detailed account of the density matrix formalism and the resolvent operator theory is given. The statistical mixture of quantum states is described in terms of the density matrix operator, a concept which in an elegant manner allows one to obtain the ensemble average of an observable [a Hermitian operator, which eigenspectrum is complete]. On the basis of an integral equation for the evolution operator, described in the Interaction Representation, the Liouville equation, describing the dynamical evolution of the density matrix operator, is established. A comprehensive analysis of thermal equilibrium in electron systems is presented. For a description of the dynamical time evolution of a system in contact with a heat bath, a reservoir in thermal equilibrium, the den- sity matrix operator approach is shown to be extremely convenient. The Kubo formalism for the time-dependent density matrix is discussed in its most general form. The so-called resolvent propagator formalism is set up starting from a discussion of the analytical part of a Dirac delta function. Having established integral equations for the retarded and advanced scalar propagator operators, the resolvent propagator concept is introduced and analyzed. The resolvent of the Hamiltonian is of particular importance in physics, and the singularities of this resolvent (poles and branch cuts) are identified. We finish by a study of correlated systems in terms of the reduced density matrix operator concept.
Abstract This chapter introduces the density operator and the Liouville equation and outlines how reduced dynamical description of open quantum systems naturally leads to the appearance of relaxation processes. (1) The density operator and the quantum Liouville equation (the density matrix for a pure system, statistical mixtures, representations, coherences, thermodynamic equilibrium). (2) An example: The time evolution of a two-level system in the density matrix formalism. (3) Reduced descriptions. (4) Time evolution equations for reduced density operators: The quantum master equation (projection operators, The Nakajima–Zwanzig equation, Derivation of the quantum master equation using the thermal projector, The quantum master equation in the interaction representation, The Markovian limit—the Redfield equation, The secular approximation and the Lindblad equation). (5) The Lindblad equation in the ‘Heisenberg representation’. (6) Relaxation of a two-level system and a harmonic oscillator revisited. (7) The optically driven two-level system in a thermal environment—the Bloch equations. (8) The oscillating dipole model of a two-level molecule. (9) Analogy of a coupled two-level system to a spin ½ system in a magnetic field.
The postulates of quantum mechanics associate the time-evolution of a system with its time-dependent Schrödinger equation. We start by examining different solutions to this equation for a particle, represented in terms of a Gaussian wave packet, in different scenarios: free, scattered from a potential energy barrier, or trapped in a potential energy well. In some cases, we encounter stationary solutions, in which the probability density does not change in time (a standing wave). These solutions are identified as eigenfunctions of a system Hamiltonian. The properties of the Hamiltonian as a Hermitian operator are introduced, and particularly, the fact that its proper eigenfunctions can compose an orthonormal set, and that the corresponding eigenvalues are real-valued. Learning that all operators that relate to measurables are Hermitian, and that their eigenvalues relate to the measured values, we conclude that the eigenvalues of the energy operator (Hamiltonian) are the energy levels of the quantum system.