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Accurate knowledge of the properties of hydrogen at high compression is crucial for astrophysics (e.g., planetary and stellar interiors, brown dwarfs, atmosphere of compact stars) and laboratory experiments, including inertial confinement fusion. There exists experimental data for the equation of state, conductivity, and Thomson scattering spectra. However, the analysis of the measurements at extreme pressures and temperatures typically involves additional model assumptions, which makes it difficult to assess the accuracy of the experimental data rigorously. On the other hand, theory and modeling have produced extensive collections of data. They originate from a very large variety of models and simulations including path integral Monte Carlo (PIMC) simulations, density functional theory (DFT), chemical models, machine-learned models, and combinations thereof. At the same time, each of these methods has fundamental limitations (fermion sign problem in PIMC, approximate exchange–correlation functionals of DFT, inconsistent interaction energy contributions in chemical models, etc.), so for some parameter ranges accurate predictions are difficult. Recently, a number of breakthroughs in first principles PIMC as well as in DFT simulations were achieved which are discussed in this review. Here we use these results to benchmark different simulation methods. We present an update of the hydrogen phase diagram at high pressures, the expected phase transitions, and thermodynamic properties including the equation of state and momentum distribution. Furthermore, we discuss available dynamic results for warm dense hydrogen, including the conductivity, dynamic structure factor, plasmon dispersion, imaginary-time structure, and density response functions. We conclude by outlining strategies to combine different simulations to achieve accurate theoretical predictions that are based on first principles.
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Bound-State Breaking and the Importance of Thermal Exchange–Correlation Effects in Warm Dense Hydrogen
Hydrogen at extreme temperatures and pressures is of key relevance for cutting-edge technological applications, with inertial confinement fusion research being a prime example. In addition, it is ubiquitous throughout our universe and naturally occurs in a variety of astrophysical objects. In the present work, we present exact ab initio path integral Monte Carlo (PIMC) results for the electronic density of warm dense hydrogen along a line of constant degeneracy across a broad range of densities. Using the well-known concept of reduced density gradients, we develop a new framework to identify the breaking of bound states due to pressure ionization in bulk hydrogen. Moreover, we use our PIMC results as a reference to rigorously assess the accuracy of a variety of exchange–correlation (XC) functionals in density functional theory calculations for different density regions. Here, a key finding is the importance of thermal XC effects for the accurate description of density gradients in high-energy-density systems. Our exact PIMC test set is freely available online and can be used to guide the development of new methodologies for the simulation of warm dense matter and beyond.
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- PAR ID:
- 10494873
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Journal of Chemical Theory and Computation
- Volume:
- 20
- Issue:
- 1
- ISSN:
- 1549-9618
- Page Range / eLocation ID:
- 68 to 78
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.jctc.3c00934
