An open-source framework for analyzing N-electron dynamics. II. Hybrid density functional theory/configuration interaction methodology
An open-source framework for analyzing N-electron dynamics. II. Hybrid density functional theory/configuration interaction methodology
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DOI：
10.1002/jcc.24896
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发表时间：
2017-10-30
影响因子：
3
通讯作者：
Tremblay, Jean Christophe
中科院分区：
文献类型：
--
作者：
Hermann, Gunter;Pohl, Vincent;Tremblay, Jean Christophe
在这篇文章中，我们将分析和可视化相关多电子动力学的框架扩展到非变分、高度可扩展的电子结构方法。具体来说，明确时间相关的电子波包被写为构型相互作用单粒子（CIS）水平上的N电子波函数的线性组合，这是从参考时间相关密度泛函理论（TDDFT）计算获得的。该过程在开源 Python 程序 detCI@ORBKIT 中实现，它扩展了我们最近发布的后处理工具箱的功能 (Hermann et al., J. Comput. Chem. 2016, 37, 1511)。根据使用原子中心高斯型基函数的标准量子化学包的输出，该框架利用混合 TDDFT/CIS 波包的多决定结构来计算基本的单电子量，例如差电子密度、瞬态电子通量密度和跃迁偶极矩。该混合方案以 LiH 中激光驱动状态选择性激发的波函数数据为基准。结果表明，只要明智地选择泛函，电子动力学的所有特征都与高级方法具有良好的定量一致性。中等大小有机发色团的宽带激发进一步证明了该方法的可扩展性。此外，随时间变化的通量密度一目了然地揭示了模拟电荷迁移过程的机械细节。 (c) 2017 年 Wiley 期刊公司。
In this contribution, we extend our framework for analyzing and visualizing correlated many-electron dynamics to non-variational, highly scalable electronic structure method. Specifically, an explicitly time-dependent electronic wave packet is written as a linear combination of N-electron wave functions at the configuration interaction singles (CIS) level, which are obtained from a reference time-dependent density functional theory (TDDFT) calculation. The procedure is implemented in the open-source Python program detCI@ORBKIT, which extends the capabilities of our recently published post-processing toolbox (Hermann et al., J. Comput. Chem. 2016, 37, 1511). From the output of standard quantum chemistry packages using atom-centered Gaussian-type basis functions, the framework exploits the multideterminental structure of the hybrid TDDFT/CIS wave packet to compute fundamental one-electron quantities such as difference electronic densities, transient electronic flux densities, and transition dipole moments. The hybrid scheme is benchmarked against wave function data for the laser-driven state selective excitation in LiH. It is shown that all features of the electron dynamics are in good quantitative agreement with the higher-level method provided a judicious choice of functional is made. Broadband excitation of a medium-sized organic chromophore further demonstrates the scalability of the method. In addition, the time-dependent flux densities unravel the mechanistic details of the simulated charge migration process at a glance. (c) 2017 Wiley Periodicals, Inc.