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Canonical averaging in the second order quantized Hamilton dynamics by extension of the coherent state thermodynamics of the harmonic oscillator.

Heatwole E, Prezhdo OV

Department of Chemistry, University of Washington, Seattle, Washington 98195-1700, USA.

A conceptually simple approximation to quantum mechanics, quantized Hamilton dynamics (QHD) includes zero-point energy, tunneling, dephasing, and other important quantum effects in a classical-like description. The hierarchy of coupled differential equations describing the time evolution of observables in QHD can be mapped in the second order onto a classical system with double the dimensionality of the original system. While QHD excels at dynamics with a single initial condition, the correct method for generating thermal initial conditions in QHD remains an open question. Using the coherent state representation of thermodynamics of the harmonic oscillator (HO) [Schnack, Europhys. Lett. 45, 647 (1999)], we develop canonical averaging for the second order QHD [Prezhdo, J. Chem. Phys. 117, 2995 (2002)]. The methodology is exact for the free particle and HO, and shows good agreement with quantum results for a variety of quartic potentials.

Published 7 June 2007 in J Chem Phys, 126(20): 204108.
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