Quantum dynamics (i.e. the Schrödinger equation) and classical dynamics (i.e. Hamilton equations) can both be formulated in equal geometric terms: a Poisson bracket defined on a manifold. In this paper, we first show that the hybrid quantum-classical dynamics prescribed by the Ehrenfest equations can also be formulated within this general framework, what has been used in the literature to construct propagation schemes for Ehrenfest dynamics. Then, the existence of a well-defined Poisson bracket allows us to arrive to a Liouville equation for a statistical ensemble of Ehrenfest systems. The study of a generic toy model shows that the evolution produced by Ehrenfest dynamics is ergodic and therefore the only constants of motion are functions of the Hamiltonian. The emergence of the canonical ensemble characterized by the Boltzmann distribution follows after an appropriate application of the principle of equal a priori probabilities to this case. Once we know the canonical distribution of an Ehrenfest system, it is straightforward to extend the formalism of Nosé (invented to do constant temperature molecular dynamics by a non-stochastic method) to our Ehrenfest formalism. This work also provides the basis for extending stochastic methods to Ehrenfest dynamics.
Quantum dynamics (i.e. the Schrödinger equation) and classical dynamics (i.e. Hamilton equations) can both be formulated in equal geometric terms: a Poisson bracket defined on a manifold. In this paper, we first show that the hybrid quantum-classical dynamics prescribed by the Ehrenfest equations can also be formulated within this general framework, what has been used in the literature to construct propagation schemes for Ehrenfest dynamics. Then, the existence of a well-defined Poisson bracket allows us to arrive to a Liouville equation for a statistical ensemble of Ehrenfest systems. The study of a generic toy model shows that the evolution produced by Ehrenfest dynamics is ergodic and therefore the only constants of motion are functions of the Hamiltonian. The emergence of the canonical ensemble characterized by the Boltzmann distribution follows after an appropriate application of the principle of equal a priori probabilities to this case. Once we know the canonical distribution of an Ehrenfest system, it is straightforward to extend the formalism of Nosé (invented to do constant temperature molecular dynamics by a non-stochastic method) to our Ehrenfest formalism. This work also provides the basis for extending stochastic methods to Ehrenfest dynamics.
Quantum dynamics (i.e. the Schrödinger equation) and classical dynamics (i.e. Hamilton equations) can both be formulated in equal geometric terms: a Poisson bracket defined on a manifold. In this paper, we first show that the hybrid quantum-classical dynamics prescribed by the Ehrenfest equations can also be formulated within this general framework, what has been used in the literature to construct propagation schemes for Ehrenfest dynamics. Then, the existence of a well-defined Poisson bracket allows us to arrive to a Liouville equation for a statistical ensemble of Ehrenfest systems. The study of a generic toy model shows that the evolution produced by Ehrenfest dynamics is ergodic and therefore the only constants of motion are functions of the Hamiltonian. The emergence of the canonical ensemble characterized by the Boltzmann distribution follows after an appropriate application of the principle of equal a priori probabilities to this case. Once we know the canonical distribution of an Ehrenfest system, it is straightforward to extend the formalism of Nosé (invented to do constant temperature molecular dynamics by a non-stochastic method) to our Ehrenfest formalism. This work also provides the basis for extending stochastic methods to Ehrenfest dynamics.
Quantum dynamics (e.g., the Schrödinger equation) and classical dynamics (e.g., Hamilton equations) can both be formulated in equal geometric terms: a Poisson bracket defined on a manifold. The difference between both worlds is due to the presence of extra structure in the quantum case, that leads to the appearance of the probabilistic nature of the measurements and the indetermination and superposition principles. In this paper we first show that the quantum-classical dynamics prescribed by the Ehrenfest equations can also be formulated within this general framework, what has been used in the literature to construct propagation schemes for Ehrenfest dynamics. Then, the existence of a well defined Poisson bracket allows to arrive to a Liouville equation for a statistical ensemble of Ehrenfest systems. The study of a generic toy model shows that the evolution produced by Ehrenfest dynamics is ergodic and therefore the only constants of motion are functions of the Hamiltonian. The emergence of the canonical ensemble characterized by the Boltzmann's distribution follows after an appropriate application of the principle of equal a priori probabilities to this case. This work provides the basis for extending stochastic methods to Ehrenfest dynamics.
We introduce the Poisson bracket operator, which is an alternative quantum counterpart of the Poisson bracket. This operator is defined using the operator derivative formulated in quantum analysis and is equivalent to the Poisson bracket in the classical limit. Using this, we derive the quantum canonical equation, which describes the time evolution of operators. In the standard applications of quantum mechanics, the quantum canonical equation is equivalent to the Heisenberg equation. At the same time, this equation is applicable to c-number canonical variables and then coincides with the canonical equation in classical mechanics. Therefore, the Poisson bracket operator enables us to describe classical and quantum behaviors in a unified way. Moreover, the quantum canonical equation is applicable to nonstandard system where the Heisenberg equation is not defined. As an example, we consider the application to the system where c-number and q-number particles coexist. The derived dynamics satisfies the Ehrenfest theorem and the energy and momentum conservations.
The symmetry properties of quantum variational principles are considered. Euler-Poincaré reduction theory is applied to the Dirac-Frenkel variational principle for Schrödinger's dynamics producing new variational principles for the different pictures of quantum mechanics (Schrödinger's, Heisenberg's and Dirac's) as well as for the Wigner-Moyal formulation. In addition, new variational principles for mixed states dynamics have been formulated. The already known geometric characterization of quantum mechanics on the complex projective space is shown to emerge naturally from the Euler-Poincaré variational principle. Semidirect-product structures are seen to produce new variational principles for Dirac's picture. \n \nOn the other hand, the variational and Hamiltonian approach to Ehrenfest expectation values dynamics is proposed. In the Lagrangian framework, the quantum variational principle for Schrödinger's dynamics is extended to account for both classical and quantum degrees of freedom. First, it is shown that the mean field model of any quantum mechanical system can be derived from a classical-quantum Euler-Poincaré Lagrangian on the direct sum Lie algebra of the Heisenberg and unitary groups. Then, the semidirect-product structure (named Ehrenfest group), is constructed using the displacement operator from the theory of coherent quantum states ( the unitary action of the Heisenberg group on the space of wavefunctions). New classical-quantum equations for Ehrenfest's expectation values dynamics are derived redefining the mean-field model Euler-Poincaré Lagrangian on the Lie algebra of the Ehrenfest group. In the Hamiltonian framework, first expectation values of the canonical observables are shown to be equivariant momentum maps for the unitary action of the Heisenberg group on quantum states. Then, the Hamiltonian structure for Ehrenfest's dynamics is shown to be Lie-Poisson for the Ehrenfest group. The variational formulation is then given a corresponding Hamiltonian structure. The classical-quantum Ehrenfest dynamics equations produce classical and quantum dynamics as special limit cases. \n \nIn the particular case of Gaussian states, expectation values couple to second order moments, so that GS are completely characterized by first and second moments. When the total energy is computed with respect to a Gaussian state, higher moments can be expressed in terms of the first two, so that the moment hierarchy closes for Gaussian states. Second moments are shown to be equivariant momentum maps for the action of the symplectic group on the space of Wigner functions. Eventually, Gaussian states are shown to possess a Lie-Poisson structure on the Jacobi group. This structure produces an energy-conserving variant of a class of Gaussian moment models that have appeared in the chemical physics literature.
Abstract This chapter focuses on Liouville’s theorem and classical statistical mechanics, deriving the classical propagator. The terms ‘phase space volume element’ and ‘Liouville operator’ are defined and an n-particle phase space probability density function is constructed to derive the Liouville equation. This is deconstructed into the BBGKY hierarchy, and radial distribution functions are used to develop n-body correlation functions. Koopman–von Neumann theory is investigated as a classical wavefunction approach. The chapter develops an operatorial mechanics based on classical Hilbert space, and discusses the de Broglie–Bohm formulation of quantum mechanics. Partition functions, ensemble averages and the virial theorem of Clausius are defined and Poincaré’s recurrence theorem, the Gibbs H-theorem and the Gibbs paradox are discussed. The chapter also discusses commuting observables, phase–amplitude decoupling, microcanonical ensembles, canonical ensembles, grand canonical ensembles, the Boltzmann factor, Mayer–Montroll cluster expansion and the equipartition theorem and investigates symplectic integrators, focusing on molecular dynamics.
We present a consistent formalism to describe the dynamics of hybrid systems with mixed classical and quantum degrees of freedom. The probability function of the system, which, in general, will be a combination of the classical distribution function and the quantum density matrix, is described in terms of its corresponding moments. We then define a hybrid Poisson bracket, such that the dynamics of the moments is ruled by an effective Hamiltonian. In particular, a closed formula for the Poisson brackets between any two moments for an arbitrary number of degrees of freedom is presented, which corrects previous expressions derived in the literature for the purely quantum case. This formula is of special relevance for practical applications of the formalism. Finally, we study the dynamics of a particular hybrid system given by two coupled oscillators, one being quantum and the other classical. Due to the coupling, specific quantum and classical properties are transferred between different sectors. In particular, the quantum sector is allowed to violate the uncertainty relation, though we explicitly show that there exists a minimum positive bound of the total uncertainty of the hybrid system.