Equation-of-motion orbital-optimized coupled-cluster doubles method with the density-fitting approximation: An efficient implementation,Journal of Computational Chemistry

当前位置： X-MOL 学术 › J. Comput. Chem. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Equation-of-motion orbital-optimized coupled-cluster doubles method with the density-fitting approximation: An efficient implementation
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2024-09-05 , DOI: 10.1002/jcc.27495
Aslı Ünal ₁ , Uğur Bozkaya ₁

Affiliation

Orbital-optimized coupled-cluster methods are very helpful for theoretical predictions of the molecular properties of challenging chemical systems, such as excited states. In this research, an efficient implementation of the equation-of-motion orbital-optimized coupled-cluster doubles method with the density-fitting (DF) approach, denoted by DF-EOM-OCCD, is presented. The computational cost of the DF-EOM-OCCD method for excitation energies is compared with that of the conventional EOM-OCCD method. Our results demonstrate that DF-EOM-OCCD excitation energies are dramatically accelerated compared to EOM-OCCD. There are almost 17-fold reductions for the

C_{5} H_{12}

molecule in an aug-cc-pVTZ basis set with the RHF reference. This dramatic performance improvement comes from the reduced cost of integral transformation with the DF approach and the efficient evaluation of the particle-particle ladder (PPL) term, which is the most expensive term to evaluate. Further, our results show that the DF-EOM-OCCD approach is very helpful for the computation of excitation energies in open-shell molecular systems. Overall, we conclude that our new DF-EOM-OCCD implementation is very promising for the study of excited states in large-sized challenging chemical systems.

中文翻译：

具有密度拟合近似的运动方程轨道优化耦合簇双精度方法：一种高效的实现

轨道优化的耦合簇方法对于具有挑战性的化学系统（如激发态）的分子性质的理论预测非常有帮助。在这项研究中，提出了一种用密度拟合（DF）方法（用 DF-EOM-OCCD 表示）的运动方程轨道优化耦合簇双精度方法的有效实现。将 DF-EOM-OCCD 方法的激发能量计算成本与传统的 EOM-OCCD 方法进行了比较。我们的结果表明，与 EOM-OCCD 相比，DF-EOM-OCCD 激发能量显着加速。C

_{5} H_{12}

。这种显著的性能改进来自于 DF 方法降低的积分变换成本以及对粒子-粒子阶梯（PPL）项的有效评估，这是评估成本最高的项。此外，我们的结果表明，DF-EOM-OCCD 方法对于开壳分子系统中激发能的计算非常有帮助。总的来说，我们得出结论，我们的新 DF-EOM-OCCD 实现对于研究大型具有挑战性的化学系统中的激发态非常有前途。

更新日期：2024-09-05

点击分享查看原文

点击收藏

公开下载

阅读更多本刊新发论文本刊介绍/投稿指南