Pushing the Limits of EOM-CCSD with Projector-Based Embedding for Excitation Energies,The Journal of Physical Chemistry Letters

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Pushing the Limits of EOM-CCSD with Projector-Based Embedding for Excitation Energies
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2017-11-02 00:00:00 , DOI: 10.1021/acs.jpclett.7b02500
Simon J. Bennie ₁ , Basile F. E. Curchod ₁ , Frederick R. Manby ₁ , David R. Glowacki _{1,

2}

Affiliation

The calculation of accurate excitation energies using ab initio electronic structure methods such as standard equation of motion coupled cluster singles and doubles (EOM-CCSD) has been cost prohibitive for large systems. In this work, we use a simple projector-based embedding scheme to calculate the EOM-CCSD excitation energies of acrolein solvated in water molecules modeled using density functional theory (DFT). We demonstrate the accuracy of this approach gives excitation energies within 0.01 eV of full EOM-CCSD, but with significantly reduced computational cost. This approach is also shown to be relatively invariant to the choice of functional used in the environment and allows for the description of systems with large numbers of basis functions (>1000) to be treated using state-of-the-art wave function methods. The flexibility of embedding to select orbitals to add to the excited-state method provides insights into the origins of the excitations and can reduce artifacts that could arise in traditional linear response time-dependent DFT (LR-TDDFT).

中文翻译：

借助基于投影仪的嵌入式激发能量来突破EOM-CCSD的极限

从头算计算精确的激发能电子结构方法（例如，运动耦合簇单双模型的标准方程式（EOM-CCSD））对于大型系统来说已经无法承受成本。在这项工作中，我们使用基于投影仪的简单嵌入方案来计算使用密度泛函理论（DFT）建模的水分子中溶解的丙烯醛的EOM-CCSD激发能。我们证明了这种方法的准确性，可以使激发能量在整个EOM-CCSD的0.01 eV范围内，但计算成本却大大降低。还显示出该方法相对于环境中使用的功能的选择相对不变，并且允许使用最新的波动函数方法描述具有大量基本函数（> 1000）的系统的描述。

更新日期：2017-11-02

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