Brueckner doubles coupled cluster method with the polarizable continuum model of solvation.
Brueckner doubles coupled cluster method with the polarizable continuum model of solvation.
复制标题
布鲁克纳将耦合簇方法与溶剂化的可极化连续介质模型结合起来。
DOI：
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发表时间：
2011
影响因子：
4.4
通讯作者：
M. Frisch
中科院分区：
文献类型：
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作者：
M. Caricato;G. Scalmani;M. Frisch
我们提出的理论和实现计算（自由）能量和分析梯度的Brueckner双（BD）耦合集团方法在溶液中，结合极化连续模型的溶剂化（PCM）。介绍了称为PTED的完整模型和称为PTE的有效近似，并通过数值示例进行了测试。还讨论了实施细节。与耦合簇单、双CCSD-PCM-PTED和CCSD-PCM-PTE方案，使用Hartree-Fock（HF）轨道的比较。结果表明，两种PTED方案基本等效，而当高频参考波函数不稳定时，BD-PCM-PTE方案优于相应的CCSD方案，具有上级性能。BD-PCM-PTE方法的计算量与气相BD方法相当，是研究溶液中具有复杂电子结构的分子体系的有效方法。
We present the theory and implementation for computing the (free) energy and its analytical gradients with the Brueckner doubles (BD) coupled cluster method in solution, in combination with the polarizable continuum model of solvation (PCM). The complete model, called PTED, and an efficient approximation, called PTE, are introduced and tested with numerical examples. Implementation details are also discussed. A comparison with the coupled-cluster singles and doubles CCSD-PCM-PTED and CCSD-PCM-PTE schemes, which use Hartree-Fock (HF) orbitals, is presented. The results show that the two PTED approaches are mostly equivalent, while BD-PCM-PTE is shown to be superior to the corresponding CCSD scheme when the HF reference wave function is unstable. The BD-PCM-PTE scheme, whose computational cost is equivalent to gas phase BD, is therefore a promising approach to study molecular systems with complicated electronic structure in solution.