TY - JOUR

T1 - Liquid-solid transition in fully ionized hydrogen at ultra-high pressures

AU - Liberatore, Elisa

AU - Pierleoni, Carlo

AU - Ceperley, D. M.

N1 - Funding Information:
We have the pleasure to thank G. Ciccotti for his invaluable support, and S. Prestipino-Giarritta and F. Saija for useful discussions about the ground state structures. Computer resources were provided by CASPUR (Italy) within the Competitive HPC Initiative, Grant No.: cmp09-837, and by the DEISA Consortium ( www.deisa.eu ), co-funded through the EU FP6 project RI-031513 and the FP7 project RI-222919, through the DEISA Extreme Computing Initiative (DECI 2009). CP is supported by the MIUR, project PRIN2007 (Grant No. fw3mjx_004) and by IIT, project SEED n.259-SIMBEDD. DMC is supported by DOE Grant No. DE-FG52-09NA29456.
Publisher Copyright:
© 2011 American Institute of Physics.

PY - 2011/5/14

Y1 - 2011/5/14

N2 - We study the phase diagram of an effective ion model of fully ionized hydrogen at ultra-high pressure. We assume that the protons interact with a screened Coulomb potential derived from a static linear response theory. This model accurately reproduces the physical properties of hydrogen for densities greater than \documentclass[12pt]{minimal}\begin{document}$\rho -{m}=10\,\text{g/cm}^3$\end{document}ρm=10g/cm3 corresponding to the range of the coupling parameter rs 0.6. The pressure range, \documentclass[12pt]{minimal}\begin{document}$P \gtrsim 20 T\text{Pa}$\end{document}P20TPa, is well beyond present experimental limitations. Assuming classical protons, we find that the zero temperature enthalpy of the perfect bcc crystal is slightly lower than for other structures at \documentclass[12pt]{minimal}\begin{document}$\rho -{m}= 12.47 \text{\,g/cm}^{3}$\end{document}ρm=12.47g/cm3 while the fcc structure gains stability at higher density. Using Monte Carlo calculations, we compute the free energy of various phases and locate the melting transition versus density. We find that on melting, bcc is energetically favored with respect to fcc over the entire range investigated. In the solid phase the system undergoes a structural transition from bcc at higher temperature to fcc at lower temperature. The free energy difference between these two structures is very small so that obtaining a quantitative estimate of this second transition line requires accuracy beyond that provided by our method. We estimate the effect of proton zero point motion on the bcc melting line for hydrogen, deuterium, and tritium by a path integral Monte Carlo method. Although zero point effects on hydrogen are large, since the two competing phases (bcc and liquid) have locally similar environments, the effect on the melting line is small; the melting temperature for hydrogen is lowered by about 10% with respect to the classical value.

AB - We study the phase diagram of an effective ion model of fully ionized hydrogen at ultra-high pressure. We assume that the protons interact with a screened Coulomb potential derived from a static linear response theory. This model accurately reproduces the physical properties of hydrogen for densities greater than \documentclass[12pt]{minimal}\begin{document}$\rho -{m}=10\,\text{g/cm}^3$\end{document}ρm=10g/cm3 corresponding to the range of the coupling parameter rs 0.6. The pressure range, \documentclass[12pt]{minimal}\begin{document}$P \gtrsim 20 T\text{Pa}$\end{document}P20TPa, is well beyond present experimental limitations. Assuming classical protons, we find that the zero temperature enthalpy of the perfect bcc crystal is slightly lower than for other structures at \documentclass[12pt]{minimal}\begin{document}$\rho -{m}= 12.47 \text{\,g/cm}^{3}$\end{document}ρm=12.47g/cm3 while the fcc structure gains stability at higher density. Using Monte Carlo calculations, we compute the free energy of various phases and locate the melting transition versus density. We find that on melting, bcc is energetically favored with respect to fcc over the entire range investigated. In the solid phase the system undergoes a structural transition from bcc at higher temperature to fcc at lower temperature. The free energy difference between these two structures is very small so that obtaining a quantitative estimate of this second transition line requires accuracy beyond that provided by our method. We estimate the effect of proton zero point motion on the bcc melting line for hydrogen, deuterium, and tritium by a path integral Monte Carlo method. Although zero point effects on hydrogen are large, since the two competing phases (bcc and liquid) have locally similar environments, the effect on the melting line is small; the melting temperature for hydrogen is lowered by about 10% with respect to the classical value.

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U2 - 10.1063/1.3586808

DO - 10.1063/1.3586808

M3 - Article

AN - SCOPUS:84870191642

VL - 134

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 18

M1 - 184505

ER -