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The same number of optimized parameters scheme for determining intermolecular interaction energies

机译:确定分子间相互作用能的相同数量的优化参数方案

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We propose the Same Number Of Optimized Parameters (SNOOP) scheme as an alternative to the counterpoise method for treating basis set superposition errors in calculations of intermolecular interaction energies. The key point of the SNOOP scheme is to enforce that the number of optimized wave function parameters for the noninteracting system is the same as for the interacting system. This ensures a delicate balance between the quality of the monomer and dimer finite basis set calculations. We compare the SNOOP scheme to the uncorrected and counterpoise schemes theoretically as well as numerically. Numerical results for second-order Moller-Plesset perturbation theory (MP2) and coupled-cluster with single, double, and approximate triple excitations (CCSD(T)) show that the SNOOP scheme in general outperforms the uncorrected and counterpoise approaches. Furthermore, we show that SNOOP interaction energies calculated using a given basis set are of similar quality as those determined by basis set extrapolation of counterpoise-corrected results obtained at a similar computational cost. (C) 2015 AIP Publishing LLC.
机译:我们提出了相同数量的优化参数(SNOOP)方案,作为在分子间相互作用能计算中处理基集叠加误差的平衡算法的替代方案。 SNOOP方案的关键是要强制非交互系统的优化波函数参数数量与交互系统的数量相同。这样可确保在单体质量和二聚体有限基数计算之间达到微妙的平衡。我们从理论上和数值上将SNOOP方案与未校正和平衡方案进行比较。二阶Moller-Plesset微扰理论(MP2)以及具有单,双和近似三重激发的耦合簇(CCSD(T))的数值结果表明,SNOOP方案总体上优于未校正和平衡的方法。此外,我们表明,使用给定的基础集计算出的SNOOP相互作用能具有与通过以相似的计算成本获得的对位校正结果的基础集外推法确定的能量相似的质量。 (C)2015 AIP Publishing LLC。

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