The fluctuation-dissipation theorem as a diagnosis and cure for zero-point energy leakage in quantum thermal bath simulations - Sorbonne Université
Article Dans Une Revue Journal of Chemical Theory and Computation Année : 2019

The fluctuation-dissipation theorem as a diagnosis and cure for zero-point energy leakage in quantum thermal bath simulations

Etienne Mangaud
Simon Huppert
Philippe Depondt
Sara Bonella
  • Fonction : Auteur
  • PersonId : 881256
Fabio Finocchi

Résumé

Quantum thermal bath (QTB) simulations reproduce statistical nuclear quantum effects via a Langevin equation with a colored random force. Although this approach has proven efficient for a variety of chemical and condensed-matter problems, the QTB, as many other semiclassical methods, suffers from zero-point energy leakage (ZPEL). The absence of a reliable criterion to quantify the ZPEL without resorting to demanding comparisons with path integral-based calculations has so far hindered the use of the QTB for the simulation of real systems. In this work, we establish a quantitative connection between ZPEL in the QTB framework and deviations from the quantum fluctuation-dissipation theorem (FDT) that can be monitored along the simulation. This provides a rigorous general criterion to detect and quantify the ZPEL without any a priori knowledge of the system under study. We then use this criterion to build an adaptive QTB method that strictly enforces the quantum FDT at all frequencies via an on-the-fly, spectrally resolved fine-tuning of the system-bath coupling coefficients. The validity of the adaptive approach is first demonstrated on a simple two-oscillator model. It is then applied to two more realistic problems: the description of the vibrational properties of a model aluminum crystal at low temperature and the simulation of the liquid-solid phase transition in a 13-atom neon cluster. In both systems, the standard QTB results are strongly altered by the ZPEL, which can be essentially eliminated using the adaptive approach.
Fichier principal
Vignette du fichier
The Fluctuation−Dissipation Theorem as a Diagnosis and Cure for Zero-Point Energy Leakage in Quantum Thermal Bath Simulations.pdf (914.84 Ko) Télécharger le fichier
Origine Fichiers produits par l'(les) auteur(s)
Loading...

Dates et versions

hal-02171352 , version 1 (02-07-2019)

Identifiants

Citer

Etienne Mangaud, Simon Huppert, Thomas Plé, Philippe Depondt, Sara Bonella, et al.. The fluctuation-dissipation theorem as a diagnosis and cure for zero-point energy leakage in quantum thermal bath simulations. Journal of Chemical Theory and Computation, 2019, 15 (5), pp.2863-2880. ⟨10.1021/acs.jctc.8b01164⟩. ⟨hal-02171352⟩
225 Consultations
353 Téléchargements

Altmetric

Partager

More