A density matrix evolution(DME) method to simulate the dynamics of quantum systems embedded in a classical environment is presented. The method is applicable when the quantum dynamical degrees of freedom can be described in a Hilbert space of limited dimensionality. The method is applied to the case of proton-transfer reactions in a fluctuating double-well potential [details are given in the following paper in this issue] and compared to other analytical and numerical solutions. The embedding of the quantum system within the classical system by using consistent equations of motion for the classical system with-proper conservation properties is discussed and applied to the one-dimensional collision of a classical particle with a quantum oscillator.
A density matrix evolution(DME) method to simulate the dynamics of quantum systems embedded in a classical environment is presented. The method is applicable when the quantum dynamical degrees of freedom can be described in a Hilbert space of limited dimensionality. The method is applied to the case of proton-transfer reactions in a fluctuating double-well potential [details are given in the following paper in this issue] and compared to other analytical and numerical solutions. The embedding of the quantum system within the classical system by using consistent equations of motion for the classical system with-proper conservation properties is discussed and applied to the one-dimensional collision of a classical particle with a quantum oscillator.
A density matrix evolution (DME) method (Berendsen, H. J. C., and Mavri, J., 1993, J. phys. Chem., 97, 13464) to simulate the dynamics of quantum systems embedded in a classical environment is applied to study the inelastic collisions of a classical particle with a five level quantum harmonic oscillator. The results are compared with the exact quantum calculations of Secrest, D., and Johnson, B. R., 1966, J. chem. Phys., 45, 4556, and with the results of classical mechanics. The DME results are between the results of the full quantum treatment and classical mechanics but closer to the latter. Furthermore, we demonstrate the time reversibility of the DME equations of motion and discuss the importance for the time reversibility of the quantum phase described by the off-diagonal elements of the density matrix.
Methods for simulating the dynamics of composite systems, where part of the system is treated quantum mechanically and its environment is treated classically, are discussed. Such quantum-classical sys- tems arise in many physical contexts where certain degrees of freedom have an essential quantum character while the other degrees of freedom to which they are coupled may be treated classically to a good approxi- mation. The dynamics of these composite systems are governed by a quantum-classical Liouville equation for either the density matrix or the dynamical variables which are operators in the Hilbert space of the quantum subsystem and functions of the classical phase space variables of the classical environment. Solutions of the evolution equations may be formulated in terms of surface-hopping dynamics involving ensembles of tra- jectory segments interspersed with quantum transitions. The surface-hopping schemes incorporate quantum coherence and account for energy exchanges between the quantum and classical degrees of freedom. Various simulation algorithms are discussed and illustrated with calculations on simple spin-boson models but the methods described here are applicable to realistic many- body environments.
Solving quantum dynamics is an exponentially difficult problem. Thus, an exact numerical solution is inaccessible for any condensed matter system.\nA promising approach is to divide the system into a quantum subsystem containing degrees of freedom which are of greater interest or those which have more profound quantum character (e.g., have smaller mass) and a classical bath containing the rest of the system.\nImposing such a partition and treating the bath classically results in quantum-classical dynamics. The quantum-classical Liouville equation is a general equation in the Hilbert space of quantum degrees of freedom while it resides in the phase space of the classical degrees of freedom.\nAny numerical solution to this equation requires representation of the quantum subsystem in some basis. Solutions to this equation have been already proposed in the subsystem, adiabatic and force bases, each with its own cons and pros.\n\nIn this work, the quantum-classical equations of motion are cast in the subsystem basis and subsequently mapped to a number of fictitious harmonic oscillators.\nThe result is quantum-classical dynamics in the mapping basis which treats both quantum and classical degrees of freedom on the same footing, i.e., in phase space. Neglecting a portion of the back reaction of the quantum-subsystem to classical bath results in an expression for the time evolution of an operator (density matrix) equal to its Poisson bracket with the Hamiltonian.\nThis equation can be solved in terms of characteristics to provide a computationally tractable method for calculating quantum-classical dynamical properties. The expressions for expectation values and correlation functions in this formalism are derived.\nCalculations on spin-boson system, barrier crossing models---the so called Tully models---and the Fenna-Mathews-Olson pigments show very good agreement between the results of this method and numerical solutions to the Schrödinger equation.
We study the back-reaction of quantum systems onto classical ones. Taking the starting point that semi-classical physics should be described at all times by a point in classical phase space and a quantum state in Hilbert space, we consider an unravelling approach, describing the system in terms of a classical-quantum trajectory. We derive the general form of the dynamics under the assumptions that the classical trajectories are continuous and the evolution is autonomous, and the requirement that the dynamics is linear and completely positive in the combined classical-quantum state. This requirement is necessary in order to consistently describe probabilities, and forces the dynamics to be stochastic when the back-reaction is non-zero. The resulting equations of motion are natural generalisations of the standard semi-classical equations of motion, but since the resulting dynamics is linear in the combined classical-quantum state, it does not lead to the pathologies which usually follow from evolution laws based on expectation values. In particular, the evolution laws we present account for correlations between the classical and quantum system, which resolves issues associated with other semi-classical approaches. In addition, despite a breakdown of predictability in the classical degrees of freedom, the quantum state evolves deterministically conditioned on the classical trajectory, provided a trade-off between decoherence and diffusion is saturated. As a result, the quantum state remains pure when conditioned on the classical trajectory. To illustrate these points, we numerically simulate a number of semi-classical toy models, including one of vacuum fluctuations as a source driving the expansion of the universe. Finally, we discuss the application of these results to semi-classical gravity, and the black-hole information problem.