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Effective classical potential for quantum statistical averages
Vijay Ganesh Sadhasivam1, Stuart C Althorpe1, Venkat Kapil1,2,3
1University of Cambridge, Yusuf Hamied Department of Chemistry, Lensfield Road, Cambridge CB2 1EW, United Kingdom.
Abstract:
We present an effective potential that allows quantum thermal expectation values of a position-dependent observable to be estimated as a classical ensemble average of the corresponding function. We follow the approach of Feynman and Hibbs but perform the mean-field treatment of quantum fluctuations about the path starting point rather than the path centroid. Furthermore, rather than performing a full variational optimization of the potential, we explore approximate functional forms that yield numerical robustness. The resulting closed-form potential is exact in the classical and harmonic limits; benchmarks against exact position distributions for one-dimensional quartic, Morse, and double-well potentials show good agreement for potentials with harmonic support.
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