We consider rigorous path integral descriptions of the dynamics of a quantum system coupled to a polyatomic environment, assuming that the latter is well approximated by classical trajectories. Earlier work has derived semiclassical or purely classical expressions for the influence functional from the environment, which should be sufficiently accurate for many situations, but the evaluation of quantum-(semi)classical path integral (QCPI) expressions has not been practical for large-scale simulation because the interaction with the environment introduces couplings nonlocal in time. In this work, we analyze the nature of the effects on a system from its environment in light of the observation [N. Makri, J. Chem. Phys. 109, 2994 (1998)] that true nonlocality in the path integral is a strictly quantum mechanical phenomenon. If the environment is classical, the path integral becomes local and can be evaluated in a stepwise fashion along classical trajectories of the free solvent. This simple “classical path” limit of QCPI captures fully the decoherence of the system via a classical mechanism. Small corrections to the classical path QCPI approximation may be obtained via an inexpensive random hop QCPI model, which accounts for some “back reaction” effects. Exploiting the finite length of nonlocality, we argue that further inclusion of quantum decoherence is possible via an iterative evaluation of the path integral. Finally, we show that the sum of the quantum amplitude factors with respect to the system paths leads to a smooth integrand as a function of trajectory initial conditions, allowing the use of Monte Carlo methods for the multidimensional phase space integral.
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14 December 2012
Research Article|
December 04 2012
Quantum-classical path integral. I. Classical memory and weak quantum nonlocality
Roberto Lambert;
Roberto Lambert
1Department of Physics,
University of Illinois
, 1110 W. Green Street, Urbana, Illinois 61801, USA
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Nancy Makri
Nancy Makri
1Department of Physics,
University of Illinois
, 1110 W. Green Street, Urbana, Illinois 61801, USA
2Department of Chemistry,
University of Illinois
, 600 S. Goodwin Avenue, Urbana, Illinois 61801, USA
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J. Chem. Phys. 137, 22A552 (2012)
Article history
Received:
September 25 2012
Accepted:
October 31 2012
Connected Content
A companion article has been published:
Quantum-classical path integral. II. Numerical methodology
Citation
Roberto Lambert, Nancy Makri; Quantum-classical path integral. I. Classical memory and weak quantum nonlocality. J. Chem. Phys. 14 December 2012; 137 (22): 22A552. https://doi.org/10.1063/1.4767931
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