Mewes Stefanie A, Plasser Felix, Dreuw Andreas
Interdisciplinary Center for Scientific Computing, Ruprecht-Karls-University, Im Neuenheimer Feld 368, 69120 Heidelberg, Germany.
J Chem Phys. 2015 Nov 7;143(17):171101. doi: 10.1063/1.4935178.
Excited-state descriptors based on the one-particle transition density matrix referring to the exciton picture have been implemented for time-dependent density functional theory. State characters such as local, extended ππ(∗), Rydberg, or charge transfer can be intuitively classified by simple comparison of these descriptors. Strong effects of the choice of the exchange-correlation kernel on the physical nature of excited states can be found and decomposed in detail leading to a new perspective on functional performance and the design of new functionals.
基于单粒子跃迁密度矩阵并参考激子图像的激发态描述符已应用于含时密度泛函理论。通过简单比较这些描述符，可以直观地对诸如局域、扩展ππ(∗)、里德堡或电荷转移等态的特征进行分类。可以发现交换关联核的选择对激发态物理性质有强烈影响，并能详细分解，从而为泛函性能和新泛函的设计提供新的视角。
