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The DFT/MRCI method
Wiley Interdisciplinary Reviews: Computational Molecular Science ( IF 11.4 ) Pub Date : 2018-10-23 , DOI: 10.1002/wcms.1394
Christel M. Marian 1 , Adrian Heil 1 , Martin Kleinschmidt 1
Affiliation  

In the past two decades, the combined density functional theory and multireference configuration interaction (DFT/MRCI) method has developed from a powerful approach for computing spectral properties of singlet and triplet excited states of large molecules into a more general multireference method applicable to states of all spin multiplicities. In its original formulation, it shows great efficiency in the evaluation of singlet and triplet excited states which mainly originate from local one‐electron transitions. Moreover, DFT/MRCI is one of the few methods applicable to large systems that yields the correct ordering of states in extended π‐systems where double excitations play a significant role. A recently redesigned DFT/MRCI Hamiltonian extends the application range of the method to bi‐chromophores such as hydrogen‐bonded or π‐stacked dimers and loosely coupled donor–acceptor systems. In conjunction with a restricted‐open shell Kohn–Sham optimization of the molecular orbitals, even electronically excited doublet and quartet states can be addressed. After a short outline of the general ideas behind this semi‐empirical method and a brief review of alternative approaches combining density functional and multireference wavefunction theory, formulae for the DFT/MRCI Hamiltonian matrix elements are presented and the adjustments of the two‐electron contributions are discussed. The performance of the DFT/MRCI variants on excitation energies of organic molecules and transition metal compounds against experimental or ab initio reference data is analyzed and case studies are presented which show the strengths and limitations of the method. Finally, an overview over the properties available from DFT/MRCI wavefunctions and further developments is given.

中文翻译:

DFT / MRCI方法

在过去的二十年中,结合密度泛函理论和多参考组态相互作用(DFT / MRCI)方法已经从一种用于计算大分子的单重态和三重态激发态光谱特性的强大方法发展成为一种适用于分子态的更通用的多参考方法。所有旋转多重性。在其原始公式中,它显示出评估单重态和三重态激发态的高效性,这些态主要来自局部单电子跃迁。此外,DFT / MRCI是适用于大型系统的少数方法之一,可在扩展π中产生正确的状态排序双重激励起着重要作用的系统。最近重新设计的DFT / MRCI哈密顿量将方法的应用范围扩展到双发色团,例如氢键或π堆叠的二聚体和松散耦合的供体-受体系统。结合分子轨道的受限开放壳Kohn-Sham优化,甚至可以解决电子激发的双峰态和四重态。在简要概述了这种半经验方法背后的一般思想并简要回顾了结合密度泛函和多参考波函数理论的替代方法之后,提出了DFT / MRCI哈密顿矩阵元素的公式,并对两电子贡献进行了调整讨论过。分析了DFT / MRCI变体对有机分子和过渡金属化合物的激发能相对于实验或从头算参考数据的性能,并进行了案例研究,这些方法表明了该方法的优势和局限性。最后,
更新日期:2018-10-23
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