A quantum-classical limit of the canonical equilibrium time correlation function for a quantum system is derived. The quantum-classical limit for the dynamics is obtained for quantum systems comprising a subsystem of light particles in a bath of heavy quantum particles. In this limit the time evolution of operators is determined by a quantum-classical Liouville operator, but the full equilibrium canonical statistical description of the initial condition is retained. The quantum-classical correlation function expressions derived here provide a way to simulate the transport properties of quantum systems using quantum-classical surface-hopping dynamics combined with sampling schemes for the quantum equilibrium structure of both the subsystem of interest and its environment.
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22 October 2004
Research Article|
October 22 2004
Quantum-classical limit of quantum correlation functions
Alessandro Sergi;
Alessandro Sergi
Chemical Physics Theory Group, Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada
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Raymond Kapral
Raymond Kapral
Chemical Physics Theory Group, Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, Germany
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J. Chem. Phys. 121, 7565–7576 (2004)
Article history
Received:
June 21 2004
Accepted:
July 30 2004
Citation
Alessandro Sergi, Raymond Kapral; Quantum-classical limit of quantum correlation functions. J. Chem. Phys. 22 October 2004; 121 (16): 7565–7576. https://doi.org/10.1063/1.1797191
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