Quantum time correlation functions are often the principal objects of interest in experimental investigations of the dynamics of quantum systems. For instance, transport properties, such as diffusion and reaction rate coefficients, can be obtained by integrating these functions. The evaluation of such correlation functions entails sampling from quantum equilibrium density operators and quantum time evolution of operators. For condensed phase and complex systems, where quantum dynamics is difficult to carry out, approximations must often be made to compute these functions. We present a general scheme for the computation of correlation functions, which preserves the full quantum equilibrium structure of the system and approximates the time evolution with quantum-classical Liouville dynamics. Several aspects of the scheme are discussed, including a practical and general approach to sample the quantum equilibrium density, the properties of the quantum-classical Liouville equation in the context of correlation function computations, simulation schemes for the approximate dynamics and their interpretation and connections to other approximate quantum dynamical methods.
The statistical mechanics of systems whose evolution is governed by mixed quantum-classical dynamics is investigated. The algebraic properties of the quantum-classical time evolution of operators and of the density matrix are examined and compared to those of full quantum mechanics. The equilibrium density matrix that appears in this formulation is stationary under the dynamics and a method for its calculation is presented. The response of a quantum-classical system to an external force which is applied from the distant past when the system is in equilibrium is determined. The structure of the resulting equilibrium time correlation function is examined and the quantum-classical limits of equivalent quantum time correlation functions are derived. The results provide a framework for the computation of equilibrium time correlation functions for mixed quantum-classical systems.
The time evolution of the correlation functions of an ensemble of anharmonic N-component oscillators with O(N) symmetry is described by a flow equation, exact up to corrections of order
1/N2. We find effective irreversibility. Nevertheless, analytical and numerical investigation reveals that the system does not reach thermal equilibrium for large times, even when
N→∞. Depending on the initial distribution, the dynamics is asymptotically stable or it exhibits growing modes which break the conditions for the validity of the 1/N expansion for large time. We investigate both classical and quantum systems, the latter being the limit of an O(N) symmetric scalar quantum field theory in zero spatial dimensions.