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

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Max Buchholz - , University of Milan (Author)
  • Erika Fallacara - , University of Milan (Author)
  • Fabian Gottwald - , University of Rostock (Author)
  • Michele Ceotto - , University of Milan (Author)
  • Frank Grossmann - , Chair of Quantum Many-Body Theory (Author)
  • Sergei D. Ivanov - , University of Rostock (Author)

Abstract

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.

Details

Original languageEnglish
Pages (from-to)231-235
Number of pages5
JournalChemical physics
Volume515
Publication statusPublished - 14 Nov 2018
Peer-reviewedYes

External IDs

Scopus 85049314936

Keywords

Keywords

  • INITIAL-VALUE REPRESENTATION, THERMAL RATE CONSTANTS, CLASSICAL TRAJECTORY SIMULATIONS, BACKWARD SEMICLASSICAL DYNAMICS, VIBRATIONAL-ENERGY, QUANTUM-SYSTEMS, CONDENSED-PHASE, MATLAB PACKAGE, ATOM TRANSFER, MECHANICS