Back
Full-text
Journal article

Inexpensive modeling of quantum dynamics using path integral generalized Langevin equation thermostats.

  • Kapil V Laboratory of Computational Science and Modelling, Institute of Materials, Ecole Polytechnique Fédérale de Lausanne, Lausanne 1015, Switzerland.
  • Wilkins DM Laboratory of Computational Science and Modelling, Institute of Materials, Ecole Polytechnique Fédérale de Lausanne, Lausanne 1015, Switzerland.
  • Lan J Department of Chemistry, University of Zürich, Zürich, Switzerland.
  • Ceriotti M Laboratory of Computational Science and Modelling, Institute of Materials, Ecole Polytechnique Fédérale de Lausanne, Lausanne 1015, Switzerland.
Show more…
  • 2020-04-04
Published in:
  • The Journal of chemical physics. - 2020
Physical and Theoretical Chemistry
General Physics and Astronomy
English The properties of molecules and materials containing light nuclei are affected by their quantum mechanical nature. Accurate modeling of these quantum nuclear effects requires computationally demanding path integral techniques. Considerable success has been achieved in reducing the cost of such simulations by using generalized Langevin dynamics to induce frequency-dependent fluctuations. Path integral generalized Langevin equation methods, however, have this far been limited to the study of static, thermodynamic properties due to the large perturbation to the system's dynamics induced by the aggressive thermostatting. Here, we introduce a post-processing scheme, based on analytical estimates of the dynamical perturbation induced by the generalized Langevin dynamics, which makes it possible to recover meaningful time correlation properties from a thermostatted trajectory. We show that this approach yields spectroscopic observables for model and realistic systems that have an accuracy comparable to much more demanding approximate quantum dynamics techniques based on full path integral simulations.
Language
  • English
Open access status
green
Identifiers
Persistent URL
https://folia.unifr.ch/global/documents/255365
Statistics
Document views: 11 File downloads:
  • fulltext.pdf: 0