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Density matrices and path integrals

Werner Krauth

Published Sep 14, 2006• 0 citations
Publisher

Abstract

Abstract In this chapter, we continue our parallel exploration of statistical and computational physics, but now move to the field of quantum mechanics, where the density matrix generalizes the classical Boltzmann distribution. The density matrix constructs the quantum statistical probabilities from their two origins: the quantum mechanical wave functions and the Boltzmann probabilities of the energy levels. The density matrix can thus be defined in terms of the complete solution of the quantum problem (wave functions, energies), but all this information is available only in simple examples, such as the free particle or the harmonic oscillator. A simple general expression exists for the density matrix only at high temperature.

DOI
10.1093/oso/9780198515357.003.0003

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Progress in mathematical physics•Jan 1, 2003•0 citations
Abstract In this chapter, we continue our parallel exploration of statistical and computational physics, but now move to the field of quantum mechanics, where the density matrix generalizes the classical Boltzmann distribution. The density matrix constructs the quantum statistical probabilities from their two origins: the quantum mechanical wave functions and the Boltzmann probabilities of the energy levels. The density matrix can thus be defined in terms of the complete solution of the quantum problem (wave functions, energies), but all this information is available only in simple examples, such as the free particle or the harmonic oscillator. A simple general expression exists for the density matrix only at high temperature.
This chapter focuses on Quantum Mechanics and Quantum Field Theory in a euclidean formulation. This means that, in general, it discusses the matrix elements of the quantum statistical operator eβH (the density matrix at thermal equilibrium), where H is the hamiltonian and β is the inverse temperature. The chapter begins by first deriving the path integral representation of matrix elements of the quantum statistical operator for hamiltonians of the simple form p 2/2m + V (q). Comparing classical statistical physics in one space dimension and quantum statistical physics of the particle, it introduces statistical correlation functions and discusses their quantum interpretation. It then explicitly calculates the path integral corresponding to a harmonic oscillator in a time-dependent external force. This result can be used to reduce the evaluation of path integrals in the case of analytic potentials to perturbation theory. The chapter shows on a first example that path integrals are especially well suited to the study of the classical limit, by relating a quantum and classical partition function. The appendix explains some general properties of the two-point function, and use the semi-classical approximation of the partition function to derive Bohr–Sommerfeld's quantization condition.
While the dynamic state of a single particle can be specified quantum mechanically in terms of its state function, any rigorous description of the state of a many-particle system would require the complete knowledge of the dynamic state functions of all the particles. That is not always possible. On the other hand, for a large number of particles in, or near, thermal equilibrium in a uniform sample, the principles of statistical mechanics may be invoked to describe the averaged expectation values of the physically observable properties of such a many-particle system. The basic concepts of the density-matrix formalism and the quantum mechanic analog of the classical Boltzmann equation commonly used for optical and magnetic resonance problems of many-particle quantum systems are introduced in this chapter. Applications of this approach to such specific problems as the resonant interaction of electromagnetic radiation with optical media of two-level atoms, nonlinear optics, and the laser rate equations and transient dynamics are discussed in this chapter. Definitions of the density operator and the density matrix Up to this point, in studying the dynamics of quantum mechanic systems, we have assumed that the state of the system can be specified in terms of a precisely known state function |Ψ〉. On the other hand, for a macroscopic medium containing many particles, it is not always possible to know the exact dynamic states of all the particles in the medium, even for physically identical particles.
We establish a rather deep relation between statistical mechanics and quantum mechanics at an imaginary time. For the quantum field theory, this implies a relation between finite temperature quantum field theory in Minkowski space and quantum field theory in Euclidean space with one compact Euclidean time direction. The quantum mechanical language being a proper formulation of statistical physics as a molecular theory is basically the study of quantum equilibrium as well as non-equilibrium systems. A quantum system found in a thermodynamic equilibrium state with an external classical system (thermostat or thermal reservoir) may be characterized by fixed values of thermodynamic parameters of the system, say, for example, temperature T , volume V and number of particles N . In this way the total energy of the thermostat is assumed to be much greater than the energy of the system. The behavior of the quantum system may be assumed to be independent of the nature of the thermostat. The most convenient object of the quantum theory to describe such non-isolated systems is the density matrix since the partition function does not determine any local thermodynamic quantities. It is for this reason that we introduced quantum mechanical and quantum statistical density matrices which are necessary to do the investigation via path integration. This enables us to make a transition to the quasi-classical approximation of quantum statistical mechanics, which, in turn, enables us to evaluate the first quantum correction to the classical Boltzmann distribution function.
Abstract The focus of Chapter 12 is the Feynman path integral formulations of quantum mechanics and quantum statistical mechanics. The connection between real-time quantum propagator and the density matrix is established via the Wick rotation, and a Trotter expansion is used to derive discrete path integral expressions for both. The continuous limit of the discrete path integral is derived to yield the functional integral formulation of the path integral. The construction of estimators and their averages for computing quantum observables is discussed. Next, the path integral is extended to incorporate Boltzmann, Fermi-Dirac, and Bose-Einstein statistics, and a useful recursive formula for the partition function is derived that accelerates convergence by building up N-body partition functions from those of smaller systems. Quantum free energies are discussed, and algorithms for the evaluation of path integrals using molecular dynamics or Monte Carlo are presented. The chapter concludes with a discussion of higher-order factorizations and ring-polymer contraction methods to reduce the computational overhead of path-integral calculations
Abstract The functional integral representation of the density matrix at thermal equilibrium in non-relativistic quantum mechanics (QM) with many degrees of freedom, in the grand canonical formulation is introduced. In QM, Hamiltonians H(p,q) can be also expressed in terms of creation and annihilation operators, a method adapted to the study of perturbed harmonic oscillators. In the holomorphic formalism, quantum operators act by multiplication and differentiation on a vector space of analytic functions. Alternatively, they can also be represented by kernels, functions of complex variables that correspond in the classical limit to a complex parametrization of phase space. The formalism is adapted to the description of many-body boson systems. To this formalism corresponds a path integral representation of the density matrix at thermal equilibrium, where paths belong to complex spaces, instead of the more usual position–momentum phase space. A parallel formalism can be set up to describe systems with many fermion degrees of freedom, with Grassmann variables replacing complex variables. Both formalisms can be generalized to quantum gases of Bose and Fermi particles in the grand canonical formulation. Field integral representations of the corresponding quantum partition functions are derived.
In quantum statistical mechanics one has the fundamental object ρ(β; x a ,x b ), a matrix entry which defines the density matrix ρl, given in the Feynman formulation by the Euclidean path integral of the preceding chapter: $$\begin{array}{*{20}{c}} {\rho {{{(\beta ;{{x}_{a}},{{x}_{b}})}}^{{\underline{\underline {def}} }}}\int_{{{{x}_{a}} = x(0)}}^{{{{x}_{b}} = x(\beta \hbar )}} {\exp ( - {{S}_{E}}(x(t))/\hbar )D[x(t)]} } \\ { = {{I}_{E}}(0,\beta \hbar ,{{x}_{a}},{{x}_{b}})} \\ \end{array}$$ (14.1.1) where β=1kT\beta = \tfrac{1}{{kT}}β=kT1​ is the inverse temperature 1T\tfrac{1}{T}T1​ up to a constant 1k\tfrac{1}{k}k1​, k being Boltzmann’s constant. From ρ one obtains the all-important partition function Ζ as a trace: $$\begin{array}{*{20}{c}} {Z = \int_{{ - \infty }}^{\infty } {\rho (\beta ;x,x)dx} } \hfill \\ { = \int_{{ - \infty }}^{\infty } {\int_{{x(0) = x}}^{{x(\beta \hbar ) = x}} {\exp ( - {{S}_{E}}(x(t))/\hbar )D[x(t)]dx.} } } \hfill \\ \end{array}$$ (14.1.2)