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Accelerated Free Energy Estimation in Ab Initio Path Integral Monte Carlo Simulations
Center for Advanced Systems Understanding (CASUS), D-02826 Görlitz, Germany; Helmholtz-Zentrum Dresden-Rossendorf (HZDR), D-01328 Dresden, Germany.
KTH, School of Electrical Engineering and Computer Science (EECS), Electrical Engineering, Space and Plasma Physics.ORCID iD: 0009-0005-9338-3163
Center for Advanced Systems Understanding (CASUS), D-02826 Görlitz, Germany; Helmholtz-Zentrum Dresden-Rossendorf (HZDR), D-01328 Dresden, Germany.
Center for Advanced Systems Understanding (CASUS), D-02826 Görlitz, Germany; Helmholtz-Zentrum Dresden-Rossendorf (HZDR), D-01328 Dresden, Germany.
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2025 (English)In: The Journal of Physical Chemistry Letters, E-ISSN 1948-7185, Vol. 16, no 41, p. 10639-10646Article in journal (Refereed) Published
Abstract [en]

We present a methodology for accelerating the estimation of the free energy from path integral Monte Carlo simulations by considering an intermediate artificial reference system where interactions are inexpensive to evaluate numerically. Using the spherically averaged Ewald interaction as this intermediate reference system for the uniform electron gas, the interaction contribution for the free energy was evaluated up to 18 times faster than the Ewald-only method. Furthermore, an extrapolation technique with respect to the quantum statistics was tested and applied to alleviate the Fermion sign problem. Combining these two techniques enabled the evaluation of the free energy for a system of 1000 electrons, where both finite-size and statistical errors are below chemical accuracy. The general procedure can be applied to systems relevant for planetary and inertial confinement fusion modeling with low to moderate levels of quantum degeneracy.

Place, publisher, year, edition, pages
American Chemical Society (ACS) , 2025. Vol. 16, no 41, p. 10639-10646
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Physical Sciences
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URN: urn:nbn:se:kth:diva-372411DOI: 10.1021/acs.jpclett.5c02193ISI: 001587943100001PubMedID: 41051799Scopus ID: 2-s2.0-105018736631OAI: oai:DiVA.org:kth-372411DiVA, id: diva2:2012009
Note

QC 20251106

Available from: 2025-11-06 Created: 2025-11-06 Last updated: 2025-11-06Bibliographically approved

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Kalkavouras, FotiosTolias, Panagiotis

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