Entwicklung eines additiven, korrigierenden Potentials für Charge-Transfer-Zustände in zeitabhängiger Dichtefunktionaltheorie

时间相关密度泛函理论中电荷转移态的附加校正势的发展

• 批准号: 56439979
• 负责人: Professor Dr. Andreas Dreuw
• 金额: --
• 依托单位: Chair of Theoretical and Computational Chemistry
• 依托单位国家: 德国
• 项目类别: Priority Programmes
• 财政年份: 2007
• 资助国家: 德国
• 起止时间: 2006-12-31 至 2012-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/56439979?language=en
• 关键词: Entwicklung; eines; additiven; korrigierenden; Potentials

Within the last ten years, time-dependent density functional theory (TDDF) has become one of the most popular methods for the calculation of excited states of medium-sized and large molecules, because it exhibits a remarkable accuracy for typical, experimentally observable excited states at a comparably low computational cost. However, excited states with charge-transfer (CT) character are described only very poorly with TDDFT limiting its general applicability substantially. The goal of the proposed project is the development of a corrective, additive, long-range potential for an improved description of CT excited states in TDDFT. The key idea is an inclusion of exact Hartree-Fock exchange at long range in combination with a distant-dependent energy shift such that the short-range properties of typical exchange-correlation (xc) potentials remain unchanged. Thereby a tedious re-fitting of standard xc-potential can be avoided, which makes our corrective potential universally applicable. The resulting ease of implementation into existing quantum chemistry program packages, will potentially lead to wide application and broad acceptance in the theoretical chemistry community.

在过去的十年里，时间依赖密度泛函数理论（TDDF）已经成为计算大中型分子激发态的最流行的方法之一，因为它以相对较低的计算成本对典型的、实验可观察到的激发态表现出惊人的准确性。然而，具有电荷转移（CT）特征的激发态描述得很差，TDDFT极大地限制了它的一般适用性。该项目的目标是为改进TDDFT中CT激发态的描述开发一种校正的、附加的、远程电位。其关键思想是在长范围内包含精确的Hartree-Fock交换，并结合与远相关的能量转移，从而使典型的交换相关（xc）势的短范围性质保持不变。从而避免了对标准xc电位进行繁琐的重新拟合，使校正电位具有普遍适用性。因此，在现有的量子化学程序包中易于实现，将有可能导致理论化学社区的广泛应用和广泛接受。