A first-principles study of helium diffusion in aragonite under high pressure up to 40 GPa

Abstract

Helium diffusion in carbonates under mantle pressure is crucial for understanding thermal and chemical evolution of mantle. Based on the density functional theory(DFT) and the the climbing image nudged elastic band (CI-NEB) method, we performed first-principles calculations of diffusion characteristics of helium in perfect aragonite crystal under high pressure to 40 GPa. Our results show that He diffusion behaviors are controlled by pressure, temperature and crystal size. The activation energy increases, and the diffusion coefficients decrease significantly under high pressure. Ea[100] increases from 176.02 kJ/mol to 278.75 kJ/mol, and Ea[001] increases from 195.89 kJ/mol to 290.43 kJ/mol, with pressure increasing from 20 GPa to 40 GPa. At 700 K, the diffusion coefficients at 40 GPa is 7 orders of magnitude lower than that at 20 GPa; and at 1000 K it decrease 5 orders of magnitude. To ensure that at least 90 % helium is not lost, we synthesized the temperature obtained from cooling and heating processes and derive the ’stable temperature range’ for helium in aragonite. The obtained results show that the stable temperature range is 22–76 ℃ at 0 GPa and 641–872 °C at 40 GPa, for the crystal of 100–2000 μm size. Besides, the travel time of helium in aragonite under high pressure increases rapidly with pressure increasing. Our calculations indicate that helium can be quantitatively retained in aragonite in the deep mantle as long as the temperature is in the ’stable temperature range’. These results have certain implications for exploring the evolution of mantle and the storage of helium within it.