The Fluctuation-Dissipation Theorem as a Diagnosis and Cure for Zero-Point Energy Leakage in Quantum Thermal Bath Simulations
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.
Medienart: |
E-Artikel |
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Erscheinungsjahr: |
2019 |
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Erschienen: |
2019 |
Enthalten in: |
Zur Gesamtaufnahme - volume:15 |
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Enthalten in: |
Journal of chemical theory and computation - 15(2019), 5 vom: 14. Mai, Seite 2863-2880 |
Sprache: |
Englisch |
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Beteiligte Personen: |
Mangaud, Etienne [VerfasserIn] |
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Anmerkungen: |
Date Revised 20.11.2019 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
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doi: |
10.1021/acs.jctc.8b01164 |
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funding: |
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Förderinstitution / Projekttitel: |
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PPN (Katalog-ID): |
NLM295609052 |
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520 | |a 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 | ||
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700 | 1 | |a Bonella, Sara |e verfasserin |4 aut | |
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