Ab initio Gibbs ensemble Monte Carlo simulations of the liquid–vapor equilibrium and the critical point of sodium

Literature Information

Publication Date 2020-12-21
DOI 10.1039/D0CP04158K
Impact Factor 3.676
Authors

Zhi Li, Christophe Winisdoerffer


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Abstract

The ab initio (ai) Gibbs ensemble (GE) Monte Carlo (MC) method coupled with Kohn–Sham density functional theory is successful in predicting the liquid–vapour equilibrium of insulating systems. Here we show that the aiGEMC method can be used to study also metallic systems, where the excited electronic states play an important role and cannot be neglected. For this we include the electronic free energy in the formulation of the effective energy of the system to be used in the acceptance criteria for the MC moves. The application of this aiGEMC method to sodium yields a good agreement with available experimental data on the liquid–vapour equilibrium densities. We predict a critical point for sodium at 2338 ± 108 K and 0.24 ± 0.03 g cm−3. The liquid structure stemming from aiGEMC simulations is very similar to the one from ab initio molecular dynamics. Since this method can determine phase transition without computing the Gibbs free energy, it may offer a new possibility to study other materials with a reasonable computational cost.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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