论文标题
MP2-F12基集收敛附近的完整基集限制：$ H $功能是否足够？
MP2-F12 basis set convergence near the complete basis set limit: are $h$ functions sufficient?
论文作者
论文摘要
我们已经使用了大参考（REF）基集的部分波截断以及标准的F12优化基集合，研究了W4-08热化学基准的标题问题。借助REF基集，I函数对总雾化能（TAES）的根平方（RMS）贡献约为0.01 kcal/mol，最大的个体贡献为0.04 kcal/mol，对于\ ce {p2}}和\ ce {p4}。但是，即使在这些情况下，基础设置从\ {g，h \}基础设置的外推也可以充分解决该问题。在$ spdfgh $ Angular Momena中，使用基集不足以饱和，可能会导致夸张的$ i $函数贡献。对于$ spdfg $和$ spdfgh $基集的外推，基集融合似乎非常接近理论渐近$ \ propto l^{ - 7} $行为。因此，我们得出的结论是，即使对于高度要求的F12应用程序，$ H $功能也足够。随着单参数外推，$ spdf $和$ spdfg $基集是足够的，aug-cc-pv \ {t，q \} z-f12产生RMSD = 0.03 kcal/mol。对CCSD（F12*）和CCSD-F12B的有限探索表明，我们的结论也适用于高级F12方法。
We have investigated the title question for the W4-08 thermochemical benchmark using partial-wave truncations of a large reference (REF) basis set, as well as for standard F12-optimized basis sets. With the REF basis set, the root mean square (RMS) contribution of i functions to the total atomization energies (TAEs) is about 0.01 kcal/mol, the largest individual contributions being 0.04 kcal/mol for \ce{P2} and \ce{P4}. However, even for these cases, basis set extrapolation from \{g,h\} basis sets adequately addresses the problem. Using basis sets insufficiently saturated in the $spdfgh$ angular momenta may lead to exaggerated $i$ function contributions. For extrapolation from $spdfg$ and $spdfgh$ basis sets, basis set convergence appears to be quite close to the theoretical asymptotic $\propto L^{-7}$ behavior. We hence conclude that $h$ functions are sufficient even for highly demanding F12 applications. With one-parameter extrapolation, $spdf$ and $spdfg$ basis sets are adequate, with aug-cc-pV\{T,Q\}Z-F12 yielding RMSD=0.03 kcal/mol. A limited exploration of CCSD(F12*) and CCSD-F12b suggests our conclusions are applicable to higher-level F12 methods as well.
