Benchmarking Excited-State Calculations Using Exciton Properties
Benchmarking Excited-State Calculations Using Exciton Properties
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DOI：
10.1021/acs.jctc.7b01145
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发表时间：
2018-02-01
影响因子：
5.5
通讯作者：
Dreuw, Andreas
中科院分区：
文献类型：
--
作者：
Mewes, Stefanie A.;Plasser, Felix;Dreuw, Andreas
基准测试是计算化学中的一项日常任务，但在不同方法之间进行有意义的比较并非易事。基准研究通常侧重于最明显的数量，如能量差异。但是，为了获得更深入的了解，我们需要解释理论方法之间的差异，即基本的波函数和物理相关的量。我们提出了一个新的策略基准激发态计算，这超出了激发能和振子强度，并涉及激子特性的分析基础上的单粒子跃迁密度矩阵。通过使用这种方法，我们比较了许多体激发态方法（运动方程耦合簇和代数图解构造）和含时密度泛函理论的性能。所选的例子说明了不同的激子描述符在指定状态字符和解释不同方法之间的差异的效用。这些例子包括里德堡态、价态和电荷转移态，以及大共轭体系中的离域激子态和具有大量双激发特性的态。
Benchmarking is an every-day task in computational chemistry, yet making meaningful comparisons between different methods is nontrivial. Benchmark studies often focus on the most obvious quantities such as energy differences. But to gain insight, it is desirable to explain the discrepancies between theoretical methods in terms of underlying wave functions and, consequently, physically relevant quantities. We present a new strategy of benchmarking excited-state calculations, which goes beyond excitation energies and oscillator strengths and involves the analysis of exciton properties based on the one-particle transition density matrix. By using this approach, we compare the performance of many body excited-state methods (equation-of-motion coupled-cluster and algebraic diagrammatic construction) and time-dependent density functional theory. The selected examples illustrate the utility of different exciton descriptors in assigning state character and explaining the discrepancies among different methods. The examples include Rydberg, valence, and charge-transfer states, as well as delocalized excitonic states in large conjugated systems and states with substantial doubly excited character.