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  4. Approximating Matsubara dynamics using the planetary model: Tests on liquid water and ice
 
research article

Approximating Matsubara dynamics using the planetary model: Tests on liquid water and ice

Willatt, Michael J.
•
Ceriotti, Michele  
•
Althorpe, Stuart C.
2018
The Journal of Chemical Physics

Matsubara dynamics is the quantum-Boltzmann-conserving classical dynamics which remains when real-time coherences are taken out of the exact quantum Liouvillian [T. J. H. Hele et al., J. Chem. Phys. 142, 134103 (2015)]; because of a phase-term, it cannot be used as a practical method without further approximation. Recently, Smith et al. [J. Chem. Phys. 142, 244112 (2015)] developed a “planetary” model dynamics which conserves the Feynman-Kleinert (FK) approximation to the quantum-Boltzmann distribution. Here, we show that for moderately anharmonic potentials, the planetary dynamics gives a good approximation to Matsubara trajectories on the FK potential surface by decoupling the centroid trajectory from the locally harmonic Matsubara fluctuations, which reduce to a single phase-less fluctuation particle (the “planet”). We also show that the FK effective frequency can be approximated by a direct integral over these fluctuations, obviating the need to solve iterative equations. This modification, together with use of thermostatted ring-polymer molecular dynamics, allows us to test the planetary model on water (gas-phase, liquid, and ice) using the q-TIP4P/F potential surface. The “planetary” fluctuations give a poor approximation to the rotational/librational bands in the infrared spectrum, but a good approximation to the bend and stretch bands, where the fluctuation lineshape is found to be motionally narrowed by the vibrations of the centroid.

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Type
research article
DOI
10.1063/1.5004808
Web of Science ID

WOS:000427517200040

Author(s)
Willatt, Michael J.
Ceriotti, Michele  
Althorpe, Stuart C.
Date Issued

2018

Published in
The Journal of Chemical Physics
Volume

148

Issue

10

Article Number

102336

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
COSMO  
Available on Infoscience
November 19, 2019
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/163190
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