Evaluation of the restricted virtual space approximation in the algebraic‐diagrammatic construction scheme for the polarization propagator to speed‐up excited‐state calculations
Evaluation of the restricted virtual space approximation in the algebraic‐diagrammatic construction scheme for the polarization propagator to speed‐up excited‐state calculations
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评估偏振传播器代数图解构造方案中的受限虚拟空间近似以加速激发态计算
DOI：
10.1002/jcc.24794
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发表时间：
2017
影响因子：
3
通讯作者：
A. Dreuw
中科院分区：
文献类型：
--
作者：
Chong Yang;A. Dreuw
有限的虚拟空间（RVS）近似的代数图解构造（ADC）计划的偏振传播器的适用性和局限性进行评估，直到三阶。在RVS‐ADC中，不仅核心，而且大量的能量高的虚轨道在低激发电子态的激发能计算中受到限制。使用辛四烯，吲哚和吡啶作为代表性的例子和不同的标准基组的三重zeta质量，RVS-ADC（2）证明是非常有用的，对ππ* 激发态的影响可以忽略不计。然而，对于nπ* 或πσ* 状态，RVS近似通常不太可靠，但在三阶ADC水平上优于二阶ADC水平。此外，引入了统一的、基组独立的、因此归一化的虚拟轨道阈值（值），使得RVS近似更可控和先验适用。© 2017 Wiley Periodicals，Inc.
The applicability and limitations of the restricted virtual space (RVS) approximation within the algebraic‐diagrammatic construction (ADC) scheme for the polarization propagator up to third order is evaluated. In RVS‐ADC, not only the core but also a substantial amount of energetically high‐lying virtual orbitals is restricted in excitation energy calculations of low‐lying excited electronic states. Using octatetraene, indole, and pyridine as representative examples and different standard basis sets of triple‐zeta quality, RVS‐ADC(2) turns out to be highly useful and to have negligible effects on ππ* excited states. However, for nπ* or πσ* states, the RVS approximation is generally less reliable but better at third‐order than second‐order ADC level. In addition, a unified, basis‐set independent, thus normalized virtual orbital threshold (value) is introduced, making the RVS approximation more controllable and a priori applicable. © 2017 Wiley Periodicals, Inc.