Design and Parameterization of a DFT/MRCI Hamiltonian for Radicals with Odd Numbers of Electrons

奇数电子自由基的 DFT/MRCI 哈密顿量的设计和参数化

• 批准号: 245515727
• 负责人: Professorin Dr. Christel M. Marian
• 金额: --
• 依托单位: Institut für Theoretische Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2013
• 资助国家: 德国
• 起止时间: 2012-12-31 至 2020-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/245515727?language=en
• 关键词: Design; Parameterization; DFT; MRCI; Hamiltonian

The primary goal of this project is to develop a cost-efficient electronic structure method that is capable of describing electronically excited states of various types (pi-pi, n-pi, Rydberg states, double excitations, charge-transfer states, ...) and spin multiplicities in a balanced manner. In the first funding period, the Hamiltonian of the combined density functional theory / multi-reference configuration interaction (DFT/MRCI) method was redesigned und reparameterized for even numbers of electrons and was shown to produce qualitatively correct results also for excimers and bi-chromophoric systems where the original DFT/MRCI Hamiltonian fails. In the second funding period, we aim at a consistent extension of our ansatz to systems with an odd number of electrons using a spinrestricted formalism. This method extension will allow to compute electronic spectra of doublet and quartet molecules as well as oxidation and ionization processes of singlet and triplet molecules at the same footing. On the application side, we set out for a comprehensive theoretical study of the electronic structure of large persistent neutral radicals that could build the basis for a new type of organic light-emitting diode emitters.

该项目的主要目标是开发一种具有成本效益的电子结构方法，能够描述各种类型的电子激发态（π-π，n-pi，Rydberg态，双激发，电荷转移态......）和自旋多重性的平衡。在第一个资助期内，结合密度泛函理论/多参考组态相互作用（DFT/MRCI）方法的哈密顿量进行了重新设计，并重新参数化为偶数电子，并显示出产生定性正确的结果，也为激子和双发色团系统，其中原始的DFT/MRCI哈密顿量失败。在第二个资助期内，我们的目标是一致的扩展，我们的anatomy系统的奇数电子使用spinrestricted形式主义。这种方法的扩展将允许计算电子光谱的双重和四重态分子以及氧化和电离过程的单线态和三线态分子在同一个立足点。在应用方面，我们着手对大的持久中性自由基的电子结构进行全面的理论研究，这可以为新型有机发光二极管发射器奠定基础。

项目成果

The DFT/MRCI method

• DOI: 10.1002/wcms.1394
• 发表时间: 2018-10
• 期刊: Wiley Interdisciplinary Reviews: Computational Molecular Science
• 作者: C. Marian;Adrian Heil;M. Kleinschmidt

DFT/MRCI Hamiltonian for odd and even numbers of electrons.

奇数和偶数电子的 DFT/MRCI 哈密顿量

• DOI: 10.1063/1.5003246
• 发表时间: 2017
• 期刊: The Journal of chemical physics
• 作者: A. Heil;C. M. Marian
• 通讯作者: C. M. Marian

DFT/MRCI-R2018 study of the photophysics of the zinc(ii) tripyrrindione radical: non-Kasha emission?

• DOI: 10.1039/c9cp04244j
• 发表时间: 2019-09
• 期刊: Physical chemistry chemical physics : PCCP
• 作者: Adrian Heil;C. Marian

The simulation of X-ray absorption spectra from ground and excited electronic states using core-valence separated DFT/MRCI.

使用核价分离 DFT/MRCI 模拟基态和激发电子态的 X 射线吸收光谱

• DOI: 10.1063/1.5110418
• 发表时间: 2019
• 期刊: The Journal of chemical physics
• 作者: I. Seidu;S. Neville;M. Kleinschmidt;A. Heil;C. M. Marian;M. Schuurman
• 通讯作者: M. Schuurman