Relativistic Correlating Basis Sets for Heavy Elements

在本工作中，我们通过三阶dougous - kroll近似考虑相对论效应，建立了从Cs到Ra的重原子（包括镧系元素）的相关CGTF集。采用分段收缩方案，使其紧凑和有效。相关cgtf的收缩系数和指数是这样确定的，以尽量减少与原子的精确NOs的差异。目前的相关集给出了98%以上的相同大小的精确NOs计算的相关能。当这些集合与MCP结合使用时，产生的相关能超过针对MCP本身优化的ANOs的99%。将该基集应用于BiH、AuH和CeO等分子体系，得到的光谱常数与实验结果非常吻合。

In this work, we developed correlating CGTF sets for heavy atoms from Cs to Ra including the Lanthanide series with considering the relativistic effect through the third-order of Douglous-Kroll approximation. A segmented contraction scheme was used for their compactness and effectiveness. The contraction coefficients and exponents of the correlating CGTFs were so determined s to minimize the difference from accurate NOs of the atoms. The present correlating sets gave more than 98% of the correlation energies calculated with the accurate NOs of the same size. When the sets were used in conjunction with MCP, the resultant correlation energies exceed 99% of those with ANOs optimized for the MCP itself. The present basis sets were used applied to molecular systems such as BiH, AuH and CeO and gave the spectroscopic constants in excellent agreement with experimental results.