Prager Stefan, Zech Alexander, Wesolowski Tomasz A, Dreuw Andreas
Interdisciplinary Center for Scientific Computing, Ruprecht-Karls University , Im Neuenheimer Feld 205A, 69120 Heidelberg, Germany.
Dèpartement de Chimie Physique, Université de Genève , 30 Quai Ernest-Ansermet, 1211 Genève, Switzerland.
J Chem Theory Comput. 2017 Oct 10;13(10):4711-4725. doi: 10.1021/acs.jctc.7b00461. Epub 2017 Sep 28.
Implementation, benchmarking, and representative applications of the new FDE-ADC(3) method for describing environmental effects on excited states as a combination of frozen density embedding (FDE) and the algebraic-diagrammatic construction scheme for the polarization propagator of third order (ADC(3)) are presented. Results of FDE-ADC(3) calculations are validated with respect to supersystem calculations on test systems with varying molecule-environment interaction strengths from dispersion up to multiple hydrogen bonds. The overall deviation compared to the supersystem calculations is as small as 0.029 eV for excitation energies, which is even smaller than the intrinsic error of ADC(3). The dependence of the accuracy on the choice of method and functional for the calculation of the environment and the nonelectrostatic part of the system-environment interaction is evaluated. In three representative examples, the FDE-ADC method is applied to investigate larger systems and to analyze excited state properties using visualization of embedded densities and orbitals.
介绍了一种新的FDE-ADC(3)方法的实现、基准测试和代表性应用，该方法将冻结密度嵌入(FDE)与三阶极化传播子的代数图解构造方案(ADC(3))相结合，用于描述环境对激发态的影响。FDE-ADC(3)计算结果通过对具有从色散到多个氢键等不同分子-环境相互作用强度的测试系统进行超系统计算来验证。与超系统计算相比，激发能的总体偏差小至0.029 eV，甚至小于ADC(3)的固有误差。评估了计算环境和系统-环境相互作用的非静电部分时，精度对方法和泛函选择的依赖性。在三个代表性示例中，FDE-ADC方法被应用于研究更大的系统，并通过嵌入密度和轨道的可视化来分析激发态性质。
