Centre for Theoretical Chemistry and Physics, The New Zealand Institute for Advanced Study, Massey University (Auckland Campus), Private Bag 102904, North Shore City, Auckland 0745, New Zealand.
J Chem Phys. 2009 Dec 28;131(24):244508. doi: 10.1063/1.3279303.
Complete basis set (CBS) limit calculations using second-order Møller-Plesset (MP2) theory for electron correlation within a many-body expansion of the interaction potential up to third order are carried out for the fcc lattices of Ne, Ar, Kr, and Xe. Lattice constants and cohesive energies from recent localized MP2 solid-state calculations by Halo et al. [Chem. Phys. Lett. 467, 294 (2009)] are in reasonable agreement with our CBS limit results. A detailed analysis reveals that MP2 severely underestimates long-range three-body effects, thus the Axilrod-Teller term is incorrectly described causing bond contractions for all rare gas solids considered. Further, any deviations in the MP2 lattice constant, cohesive energy, and bulk modulus can be traced back to inaccuracies in the binding energy and equilibrium distance of the rare gas dimer. Without inclusion of phonon dispersion, MP2 prefers the hcp over the fcc crystal structure for all rare gas solids considered.
使用多体展开的二级 Møller-Plesset (MP2) 理论进行电子相关，对 Ne、Ar、Kr 和 Xe 的 fcc 晶格进行完全基组 (CBS) 极限计算。Halo 等人最近在局域 MP2 固态计算中得到的晶格常数和内聚能[Chem. Phys. Lett. 467, 294 (2009)]与我们的 CBS 极限结果相当吻合。详细分析表明，MP2 严重低估了长程三体效应，因此 Axilrod-Teller 项被错误描述，导致所有考虑的稀有气体固体的键收缩。此外，MP2 晶格常数、内聚能和体弹性模量的任何偏差都可以追溯到稀有气体二聚体的结合能和平衡距离的不准确性。不考虑声子色散，MP2 优先选择 hcp 而不是 fcc 晶体结构，适用于所有考虑的稀有气体固体。
