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.

该项目的目的是为耦合团簇方法CC2和相关的ADC(2)、CIS(Dinf)和CIS(D)方法及其自旋成分尺度的SCS和SOS变体开发有效和通用的导体类屏蔽模型(COSMO)和原子可极化嵌入模型(PE)。对于实现，我们将利用这两种方法是自洽反应场模型的特例，并且可以被转换到共同的工作流和程序结构中。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，该场势是量子系统中的单电子算符和电子密度的泛函。在这两种情况下，都应包括嵌入电势随量子系统对外部电磁场的响应而发生的变化。对于像Cosmo这样的连续统溶剂化模型，这一点在参考文献中得到了说明。[1，2]。对于PE模型，嵌入势的响应贡献已经包含在其原始公式中[3]。嵌入势的单电子形式及其对密度和对微扰的响应的依赖性决定了嵌入电子结构计算的算法和工作流程。除了单光子和双光子UV/Vis跃迁的垂直激发能量和强度外，还应包括单光子和双光子圆二向色性的旋转强度、磷光寿命以及电子基态和激发态中的一、二和三阶性质和梯度。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。为了验证这两种嵌入方法的有效性，需要编写一个包含实验和理论参考数据的测试集，并将COSMO和PE嵌入模型在相关波函数方法CC2、ADC(2)、CIS(Dinf)和CIS(D)之间的相互作用中的性能进行基准测试。