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，含时密度泛函理论(TDDF)已经成为计算中大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代价对典型的实验可观测的激发态表现出显著的精度。然而，对具有电荷转移(CT)性质的激发态的描述很少，TDDFT极大地限制了它的普遍适用性。该项目的目标是开发一种修正的、可加性的、长程势，以改进对TDDFT中CT激发态的描述。其核心思想是包含了长程精确的Hartree-Fock交换，并结合了依赖于距离的能量移动，使得典型的交换-关联(XC)势的短程性质保持不变。因此，可以避免对标准XC势进行繁琐的重新拟合，从而使我们的校正势普遍适用。由此产生的易于在现有量子化学程序包中实施的结果，将有可能导致理论化学界的广泛应用和广泛接受。