Department of Chemistry and Ames Laboratory USDOE, Iowa State University, Ames, Iowa 50011, USA.
J Chem Phys. 2010 Feb 21;132(7):074109. doi: 10.1063/1.3298373.
The recently introduced method of correlation energy extrapolation by intrinsic scaling is used to calculate the nonrelativistic electron correlations in the valence shell of the O(2) molecule at 24 internuclear distances along the ground state (3)Sigma(g)(-) potential energy curve from 0.9 to 6 A, the equilibrium distance being 1.207 52 A. Using Dunning's correlation-consistent triple- and quadruple-zeta basis sets, the full configuration interaction energies are determined, with an accuracy of about 0.3 mhartree, by successively generating up to sextuple excitations with respect to multiconfigurational reference functions that strongly change along the reaction path. The energies of the reference functions and those of the correlation energies with respect to these reference functions are then extrapolated to their complete basis set limits.
最近引入的通过内禀标度进行相关能量外推的方法被用于计算 O(2)分子价壳层中的非相对论电子相关，沿着基态 (3)Sigma(g)(-)势能曲线在 24 个核间距处进行计算，核间距从 0.9 到 6 A，平衡距离为 1.207 52 A。使用 Dunning 的相关一致的三重和四重 zeta 基组，通过连续生成多达六重相对于多组态参考函数的激发，确定了全组态相互作用能，精度约为 0.3 mhartree，这些参考函数沿着反应路径强烈变化。然后将参考函数的能量和相对于这些参考函数的相关能量的能量外推到它们的完全基组极限。
