Modelling one- and two-photon spectroscopy in solution with the coupled-cluster model CC2 combined with continuum and atomistic embedding models

使用耦合团簇模型 CC2 结合连续介质和原子嵌入模型对溶液中的一光子和双光子光谱进行建模

• 批准号: 317213500
• 负责人: Professor Dr. Christof Hättig
• 金额: --
• 依托单位: Lehrstuhl für Theoretische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2016
• 资助国家: 德国
• 起止时间: 2015-12-31 至 2022-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/317213500?language=en
• 关键词: Modelling; two; photon; spectroscopy; solution

The aim of the project is the development of an efficient and general implementation of the Conductor-like screening model (COSMO) and the atomistic polarizable embedding model (PE) for the coupled-cluster method CC2 and the related ADC(2), CIS(Dinf) and CIS(D) methods including their spin-component scaled SCS and SOS variants. For the implementation we will exploit that both approaches are special cases of a self-consistent reaction field model and can be casted into a common work flow and program structure. In both approaches the interaction between the electrons and the environment is described through an embedding or reaction field potential which is a one-electron operator and a functional of the electron density in the quantum system. In both cases the changes of the embedding potential upon changes in the quantum system as response to an externally applied electromagnetic field should be included. For continuum solvation models like COSMO this was shown in Refs. [1,2]. For the PE model the response contributions to the embedding potential were already included by construction in its original formulation [3].The one-electron form of the embedding potential and its dependence on the density and its response to perturbations determines the algorithms and the workflow of the embedded electronic structure calculation. The implementation should comprise in addition to vertical excitation energies and intensities for one- and two-photon UV/Vis transitions also rotatory strengths for one- and two-photon circular dichroism, phosphorescence lifetimes, and first-, second- and third-order properties and gradients in the electronic ground and in excited states. It should be integrated into the MPI and OpenMP parallel versions for use on distributed and shared memory computer systems. The limitations of already existing program parts to closed-shell Hartree-Fock references should be removed.To validate the two embedding approaches, a test set with experimental and theoretical reference data should be compiled and the performance of the COSMO and PE embedding models in the interplay with the correlated wavefunction methods CC2, ADC(2), CIS(Dinf), and CIS(D) benchmarked for the implemented properties.

该项目的目标是为耦合簇方法 CC2 和相关 ADC(2)、CIS( Dinf) 和 CIS(D) 方法，包括其自旋分量缩放的 SCS 和 SOS 变体。在实现过程中，我们将利用这两种方法都是自洽反应场模型的特殊情况，并且可以转化为通用的工作流程和程序结构。在这两种方法中，电子与环境之间的相互作用都是通过嵌入或反应场势来描述的，该势是单电子算符，并且是量子系统中电子密度的函数。在这两种情况下，应包括量子系统响应于外部施加的电磁场而变化时嵌入电势的变化。对于像 COSMO 这样的连续溶剂化模型，这在参考文献中显示。 [1,2]。对于 PE 模型，对嵌入势的响应贡献已通过构建包含在其原始公式中 [3]。嵌入势的单电子形式及其对密度的依赖性及其对扰动的响应决定了算法和工作流程嵌入式电子结构计算。除了单光子和双光子紫外/可见光跃迁的垂直激发能量和强度之外，该实现还应包括单光子和双光子圆二色性的旋转强度、磷光寿命以及一阶、二阶和三阶特性以及电子基态和激发态的梯度。它应该集成到 MPI 和 OpenMP 并行版本中，以便在分布式和共享内存计算机系统上使用。应消除现有程序部分对闭壳 Hartree-Fock 参考的限制。为了验证这两种嵌入方法，应编译具有实验和理论参考数据的测试集，并在与针对所实现的属性进行基准测试的相关波函数方法 CC2、ADC(2)、CIS(Dinf) 和 CIS(D) 的相互作用。