Herman-Kluk propagator is free from zero-point energy leakage

Quasiclassical techniques constitute a promising route to approximate quantum dynamics based on classical trajectories starting from a quantum-mechanically correct distribution. One of their main drawbacks is the so-called zero-point energy (ZPE) leakage, that is artificial redistribution of energy...

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Bibliographic Details
Published in:Chemical physics 2018-11, Vol.515, p.231-235
Main Authors: Buchholz, Max, Fallacara, Erika, Gottwald, Fabian, Ceotto, Michele, Grossmann, Frank, Ivanov, Sergei D.
Format: Article
Language:English
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Summary:Quasiclassical techniques constitute a promising route to approximate quantum dynamics based on classical trajectories starting from a quantum-mechanically correct distribution. One of their main drawbacks is the so-called zero-point energy (ZPE) leakage, that is artificial redistribution of energy from the modes with high frequency and thus high ZPE to those with low frequency and ZPE due to classical equipartition. Here, we show that the elaborate semiclassical formalism based on the Herman-Kluk propagator is free from the ZPE leakage despite utilizing purely classical propagation. We demonstrate this with example applications for two- and three-dimensional anharmonically coupled oscillators. This finding opens the road to correct dynamical simulations of systems with a multitude of degrees of freedom that cannot be treated fully quantum-mechanically due to the exponential increase of the numerical effort.
ISSN:0301-0104
DOI:10.1016/j.chemphys.2018.06.008