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arXiv · 1807.02074

Mean-field Matsubara dynamics: Analysis of path-integral curvature effects in rovibrational spectra

George Trenins·Stuart C. Althorpe
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Abstract

It was shown recently that smooth and continuous "Matsubara" phase-space loops follow a quantum-Boltzmann-conserving classical dynamics when decoupled from non-smooth distributions, which was suggested as the reason that many dynamical observables appear to involve a mixture of classical dynamics and quantum Boltzmann statistics. Here we derive a mean-field version of this "Matsubara dynamics" which sufficiently mitigates its serious phase problem to permit numerical tests on a two-dimensional "champagne-bottle" model of a rotating OH bond. The Matsubara-dynamics rovibrational spectra are found to converge toward close agreement with the exact quantum results at all temperatures tested (200-800 K), the only significant discrepancies being a temperature-independent 22 cm$^{-1}$ blue-shift in the position of the vibrational peak and a slight broadening in its line shape. These results are compared with centroid molecular dynamics (CMD) to assess the importance of non-centroid fluctuations. Above 250 K, only the lowest-frequency non-centroid modes are needed to correct small CMD red-shifts in the vibrational peak; below 250 K, more non-centroid modes are needed to correct large CMD red-shifts and broadening. The transition between these "shallow curvature" and "deep curvature" regimes happens when imaginary-time Feynman paths become able to lower their actions by cutting through the curved potential surface, giving rise to artificial instantons in CMD.

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George Trenins, Stuart C. Althorpe. 2018-07-05. Mean-field Matsubara dynamics: Analysis of path-integral curvature effects in rovibrational spectra. https://doi.org/10.1063/1.5038616

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