论文标题
电子激发态的密度功能理论
Density Functional Theory for Electronic Excited States
论文作者
论文摘要
本章为密度功能理论(DFT)的激发状态扩展提供了基本介绍,包括其线性响应及其明确时间依赖时间的表述中的时间依赖性(TD-)DFT。正如应用于Kohn-Sham DFT基态的,线性响应理论在单独激发的Slater决定因素的基础上为激发能提供了特征值类型的问题,尽管它的频率范围格式,但还是被广泛称为“ TDDFT”。由于低成本和合理的精度的有利组合,这种TDDFT形式是激发态的大多广泛使用的量子化学方法。本章调查了线性响应TDDFT的准确性,该线性响应TDDFT通常对与地面DFT相比的交换相关功能的细节更敏感,还描述了这种方法所表现出的一些已知的系统性问题。其中一些问题可以使用轨道优化的,激发态的自洽场(SCF)计算逐案纠正,这是在所谓的激发型Kohn-Sham理论或“ Delta-SCF”过程中,包括一类方法,其中包括受限制的开放式Kohn-Sham理论。这些方法的最新成功得到了强调,包括双重激发和核心水平的激发。最后,根据时间依赖性的Schroedinger方程的Kohn-Sham类似物,明确的时间依赖性(或“实时”)TDDFT涉及在外部扰动后时间繁殖分子轨道的传播。时间依赖性方法已用于建模强场电子动力学,在弱场极限中,它根据偶极矩函数的时间演变为宽带光谱提供了途径。这对于描述高能激发(如X射线光谱)以及在状态密度高的系统中很有用,如一些示例所示。
This chapter provides a basic introduction to excited-state extensions of density functional theory (DFT), including time-dependent (TD-)DFT in both its linear-response and its explicitly time-dependent formulations. As applied to the Kohn-Sham DFT ground state, linear-response theory affords an eigenvalue-type problem for the excitation energies in a basis of singly-excited Slater determinants, and is widely known simply as "TDDFT" despite its frequency-domain formulation. This form of TDDFT is the mostly widely-used quantum-chemical method for excited states, due to a favorable combination of low cost and reasonable accuracy. The chapter surveys the accuracy of linear-response TDDFT, which is generally more sensitive to the details of the exchange-correlation functional as compared to ground-state DFT, and also describes some known systemic problems exhibited by this approach. Some of those problems can be corrected on a case-by-case basis using orbital-optimized, excited-state self-consistent field (SCF) calculations, in what is known as excited-state Kohn-Sham theory or a "Delta-SCF" procedure, a class of methods that includes restricted open-shell Kohn-Sham theory. Recent successes of these approaches are highlighted, including double excitations and core-level excitations. Finally, explicitly time-dependent (or "real-time") TDDFT involves propagation of the molecular orbitals in time following an external perturbation, according to the Kohn-Sham analogue of the time-dependent Schroedinger equation. The time-dependent approach has been used to model strong-field electron dynamics, and in the weak-field limit it provides a route to broadband spectra based on the time evolution of the dipole moment function. This is useful for describing high-energy excitations (as in x-ray spectroscopy) and in systems where the density of states is high, as demonstrated by a few examples.