Three-body potential and third virial coefficients for helium including relativistic and nuclear-motion effects†
The non-additive three-body interaction potential for helium was computed using the coupled-cluster theory and the full configuration interaction method. The obtained potential comprises an improved nonrelativistic Born–Oppenheimer energy and the leading relativistic and nuclear-motion corrections. The mean absolute uncertainty of our calculations due to the incompleteness of the orbital basis set was determined employing complete-basis-set extrapolation techniques and was found to be 1.2%. For three helium atoms forming an equilateral triangle with the side length of 5.6 bohr – a geometry close to the minimum of the total potential energy surface – our three-body potential amounts to −90.6 mK, with an estimated uncertainty of 0.5 mK. An analytic function, developed to accurately fit the computed three-body interaction energies, was chosen to correctly describe the asymptotic behavior of the three-body potential for trimer configurations corresponding to both the three-atomic and the atom-diatom fragmentation channels. For large triangles with sides r12, r23, and r31, the potential takes correctly into account all angular terms decaying as r−l12 r−m23 r−n21 with l + m + n ≤ 14 for the nonrelativistic Born–Oppenheimer energy and l + m + n ≤ 9 for the post-Born–Oppenheimer corrections. We also developed a short-range analytic function describing the local behavior of the total uncertainty of the computed three-body interaction energies. Using both fits we calculated the third pressure and acoustic virial coefficients for helium and their uncertainties for a wide range of temperatures. The results of these calculations were compared with available experimental data and with previous theoretical determinations. The estimated uncertainties of present calculations are 3–5 times smaller than those reported in the best previous works.
- This article is part of the themed collection: 2023 PCCP HOT Articles