Garberoglio Giovanni, Harvey Allan H, Jeziorski Bogumił
European Centre for Theoretical Studies in Nuclear Physics and Related Areas (FBK-ECT*), Trento I-38123, Italy.
Applied Chemicals and Materials Division, National Institute of Standards and Technology, Boulder, Colorado 80305, USA.
J Chem Phys. 2021 Dec 21;155(23):234103. doi: 10.1063/5.0077684.
We present a rigorous framework for fully quantum calculation of the third dielectric virial coefficient C(T) of noble gases, including exchange effects. The quantum effects are taken into account with the path-integral Monte Carlo method. Calculations employing state-of-the-art pair and three-body potentials and pair polarizabilities yield results generally consistent with the few scattered experimental data available for helium, neon, and argon, but rigorous calculations with well-described uncertainties will require the development of surfaces for the three-body nonadditive polarizability and the three-body dipole moment. The framework, developed here for the first time, will enable new approaches to primary temperature and pressure metrology based on first-principles calculations of gas properties.
我们提出了一个用于对包括交换效应在内的稀有气体的第三维里系数C(T)进行全量子计算的严格框架。采用路径积分蒙特卡罗方法考虑量子效应。使用最先进的二体和三体势以及二体极化率进行的计算得出的结果，总体上与氦、氖和氩现有的少量零散实验数据一致，但要进行具有精确描述不确定性的严格计算，将需要开发三体非加和极化率和三体偶极矩的相关曲面。本文首次开发的该框架，将基于气体性质的第一性原理计算，为初级温度和压力计量带来新方法。
