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CRC Press eBooks

Density matrices

Bruno Juliá Díaz, Arnau Rios Huguet, Héctor Briongos Merino, Javier Rozalén Sarmiento, Artur Polls Martí

Published Sep 17, 2025• 0 citations
Publisher

Abstract

This chapter delves into the concept of density matrices, a fundamental tool in quantum mechanics for describing the state of a many-body system. Density matrices provide a compact and powerful representation of quantum states, encompassing both pure and mixed states. The study of one-body and two-body density matrices is particularly important for understanding the behavior of many-body systems, especially in contexts like quantum gases, solid-state physics, and quantum chemistry. These matrices encapsulate information about particle distributions and correlations, enabling the derivation of key properties such as energy, momentum, and entropy.

DOI
10.1201/9781003191339-11

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This chapter delves into the concept of density matrices, a fundamental tool in quantum mechanics for describing the state of a many-body system. Density matrices provide a compact and powerful representation of quantum states, encompassing both pure and mixed states. The study of one-body and two-body density matrices is particularly important for understanding the behavior of many-body systems, especially in contexts like quantum gases, solid-state physics, and quantum chemistry. These matrices encapsulate information about particle distributions and correlations, enabling the derivation of key properties such as energy, momentum, and entropy.
Abstract The fundamentals of the theory of density matrices are reviewed. The density matrix is introduced first in terms of state vectors for pure states over which a probability distribution is given. It is then shown that the applications of the density matrix do not require knowledge of the particular probability distribution over pure states that may have been used for its original determination. It is stressed that density matrices, like state vectors, describe ensembles rather than single systems, as determinism in quantum theory (except for some conservation laws) is of a statistical character only. The entropy of a quantum‐mechanical system is defined as the average per system of the entropy of an ensemble of systems described by the quantum‐mechanical (pure or mixed) state. For pure states this entropy is zero, in agreement with the fact that state vectors constitute the maximal information that can be given about a quantum‐mechanical system. As the entropy should be independent of the particular probability distribution over pure states that may have been used to form the mixed state, it is calculated from statistical considerations about an imaginary ensemble in which the eigenvalues of the density matrix are probabilities over pure states given by the eigenfunctions of the density matrix. The entropy is calculated for a mixture of two nonorthogonal states. The time evolution of the density matrix, in general, is not a unitary transformation, as observable systems are not closed and therefore in the Hamiltonian contain unknown external parameters that are not the same for the entire mixture. Therefore transitions between pure states and mixed states take place. Those from pure to mixed states take place spontaneously and irreversibly under increase of entropy. Transitions from mixed states to pure states can be fabricated; an example is given. As Wigner's thought experiment of mixing coherently the two beams from a Stern‐Gerlach apparatus according to estimates of Bohm should be impossible by loss of coherence in the gradient magnetic field, it is indicated how Wigner's ideas may be realized by using, instead, polarized light beams from birefringent crystals. After a brief review of the quantum theory of measurements and the various arguments usually given for the reducibility of state after the measurement, Wigner's argument against blind use of these arguments is interpreted as a limit of validity of the familiar probability rule of quantum theory, which should not be applied after an unsuccessful measurement. By splitting light beams coherently by glass plates, one can by the same apparatus have measurements both of the relative intensities of two coherent beams, and of interference effects between the two beams. This shows that complementarity applies to the individual systems in the beam, as they reach the glass plate where a choice must be made between two complementary possibilities of future measurement. Finally, by describing Schrödinger's cat by a density matrix and asking about its time dependence, it is shown that, if it were possible to measure the interference effects between living and dead cats used by some people as a justification for writing down a state vector for the cat, then this measurement could be used to revive some dead cats.
Along with an elementary description of the well-known density matrix formalism and of its application to the description of quantum-statistical ensembles, this chapter includes the proofs of a few propositions that are especially useful for understanding most of the developments. In the new formulation, ensembles are directly described by density matrices, observables are still described by Hermitean operators, and the rules giving the statistical distribution and the mean values of the predicted measurement results are, respectively, expressions. When stated in this manner, the rules of quantum mechanics apply directly not only to pure states but also to mixtures. This is a distinct advantage. In the case of mixtures defined by their density matrices, the new formulation also has another merit. If two proper mixtures are described by the same density matrix, any state vector representing a subensemble of one of these mixtures can be expressed as a linear combination of the state vectors representing the subensembles of the other mixture.
Abstract This chapter introduces density operators and matrices for many-body systems, and explains their reduction to one- and two-body densities. Starting from the Slater determinant, the latter are explicitly calculated for independent fermions. For such systems, the classical limit is discussed and formulas for partition function, free energy, and entropy are derived by introducing and employing the concept of Wigner transformations. The propagation of wave packets is described in one dimension, a case for which correspondence rules are derived for various combinations of quantum operators. Finally, formulas are given for the equilibrium distribution of the quantal oscillator and the associated Wigner function.
A Tribute to A. John Coleman - The Tame Mathematician.- Reduced Density Matrices: 1929-1989.- Some Aspects on the Development of the Theory of Reduced Density Matrices and the Representability Problem.- Representability Conditions.- On the Diagonal N-Representability Problem.- Fermion N-Representability Conditions Generated by a Decomposition of the 1-Particle Identity Operator onto Mutually Orthogonal Projection Operators.- The Unitarily Invariant Decomposition of Hermitian Operators.- Building Up N-Electron States with Symplectic Symmetry.- Time Dependent Antisymmetrized Geminal Power Theory Using a Coherent State Formulation.- Griffiths Inequalities for Fermion Systems.- Entropy of Reduced Density Matrices.- A Lower Bound to the Ground State Energy of a Boson System With Fermion Source.- Reduced Density Operators, Their Related von Neumann Density Operators, Close Cousins of These, and Their Physical Interpretation.- Theory and Practice of the Spin-Adapted Reduced Hamiltonians (SRH).- Variational Principle with Built-In Pure State N-Representability Conditions. The N-Electron Case.- Wigner Distributions as Representations of the Density Matrix.- Inter-Relationships Between Various Representations of One-Matrices and Related Densities: A Road Map and an Example ..- Current Problems in Density Functional Theory.- The Interface Between Reduced Density Matrices and Density Functional Theory.- The Physics Underlying the Langreth-Mehl Scheme for Non-Uniform Systems.- Understanding Energy Differences in Density Functional Theory.- Density Functional Calculations of Molecular Bond Energies.- Non-Local Effects on Atomic and Molecular Correlation Energies Studied with a Gradient-Corrected Density Functional.- An Evaluation of Local Electron Correlation Corrections and Non-Local Exchange Corrections to the Hartree-Fock-Slater Method from Calculations on Bond Energies and Electronic Spectra of Molecular Systems.- Correlation Energy Functionals of One-Matrices and Hartree-Fock Densities.- Some Remarks on Scaling Relations in Density Functional Theory.- Deduction of Semiempirical MO Methods from Density Functional Theory.- Charge and Spin Densities in Molecular Solids: Local Density Functional Calculations Versus Experiment.- A Functional of the Two-Particle Density Matrix for the Approximate Calculation of the Electronic Correlation Energy.- Extracules, Intracules, Correlation Holes, Potentials, Coefficients and All That.- The Exact Schroedinger Equation for the Electron Density.- Adiabatic Separation, Broken Symmetries and Geometry Optimization.- Asymptotic Results for Density Matrices and Electron Density in Atoms and Nearly Spherical Molecules.- An Algorithm for Calculating Isoelectronic Changes in Energies, Densities, and One-Matrices.- Atoms and Ions in the Limit of Large Nuclear Charge.- Improved Thomas-Fermi Theory for Atoms.- A Bond Energy from Quantum Mechanics.- Measured Electron Densities and Band Structure Calculations.- X-ray Orthonormal Orbital Model for Crystallography.
Abstract In this chapter we discuss statistical mixtures of pure quantum states, resulting in so-called mixed states, and their representation using density operators. The properties of density operators for pure and mixed states are analysed and we examine their time evolution governed by the Liouville-von Neumann equation. As particular examples of interest we consider the density operators for thermal states, focusing on harmonic oscillators and the application of this model to calculate the average photon number for the modes of the electromagnetic field at thermal equilibrium. We then turn to two-level systems, or qubits, which are of particular relevance in quantum information theory and we inspect the geometry of the state space of density operators as a convex subspace of the Hilbert-Schmidt space. Finally, we take a closer look at density operators for bipartite systems which forms the mathematical basis for considering entanglement in later chapters.