Antusek Andrej, Jaszuński Michał, Rizzo Antonio
Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01224 Warsaw, Poland.
J Chem Phys. 2007 Feb 21;126(7):074303. doi: 10.1063/1.2446955.
The interaction-induced contribution to the NMR shielding constants in homonuclear A2 and heteronuclear AB (A,B=He,Ne,Ar) dimers is obtained ab initio by employing a coupled cluster singles and doubles with perturbative treatment of triples wave function model and extended correlation-consistent basis sets. The second virial coefficients entering the expansion of the property with the density are then computed in a fully quantum mechanical approach, for temperatures ranging from the limit of dissociation of the dimer to well above standard conditions. The results can be used to describe the density and temperature dependence of the shielding constants in binary mixtures of helium, neon, and argon. The predicted effects should be observable for the interaction of 21Ne with other rare gases.
通过采用包含三重激发微扰处理的耦合簇单双激发波函数模型和扩展的相关一致基组，从头算得到了同核A₂和异核AB（A、B = He、Ne、Ar）二聚体中相互作用诱导对核磁共振屏蔽常数的贡献。然后，采用完全量子力学方法计算了进入该性质随密度展开式的第二维里系数，温度范围从二聚体解离极限到远高于标准条件。这些结果可用于描述氦、氖和氩二元混合物中屏蔽常数的密度和温度依赖性。对于²¹Ne与其他稀有气体的相互作用，预测的效应应该是可观测的。
