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.

在过去的十年中，时间依赖性密度功能理论（TDDF）已成为计算中型和大分子激发态的最流行方法之一，因为它在相当低的计算成本下表现出了典型的，实验可观察到的激发态的显着准确性。但是，具有电荷转移（CT）特征的激发态仅描述了TDDFT的较差，从而大大限制了其一般适用性。拟议项目的目的是开发纠正性，添加剂，远程潜力，以改善TDDFT中CT激发态的描述。关键思想是将精确的Hartree-fock交换远距离结合在一起，并结合遥远的能量转移，使得典型交换 - 相关（XC）电势的短距离性能保持不变。因此，可以避免乏味的标准XC潜在电位重新安装，这使我们的纠正潜力普遍适用。由此产生的易于实施到现有的量子化学计划包中，可能会导致理论化学界的广泛应用和广泛接受。