An open‐source framework for analyzing N‐electron dynamics. I. Multideterminantal wave functions
An open‐source framework for analyzing N‐electron dynamics. I. Multideterminantal wave functions
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DOI：
10.1002/jcc.24792
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发表时间：
2017-01
影响因子：
3
通讯作者：
Vincent Pohl;G. Hermann;J. Tremblay
中科院分区：
文献类型：
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作者：
Vincent Pohl;G. Hermann;J. Tremblay
本文的目的是提供一个框架，用于分析和可视化分子系统的相关多电子动力学，其中显式依赖于时间的电子波包被表示为N电子波函数的线性组合。感兴趣的中心量是电子通量密度，它包含关于瞬时电子密度、相关相位和它们的时间演化的所有信息。它是通过使用斯莱特-康登规则约化多行列式、多电子波包，从相关的单电子算符计算出来的。在这里，我们介绍了一个通用的后处理工具-相互作用波函数在不同的理论水平上获得的多行列式组态。它被量身定做，使用以原子为中心的高斯型基函数直接从标准量子化学程序包的输出中提取数据。该过程在开放源码的Python程序DetCI@ORBKIT中实现，该程序共享并构建了我们最近发布的后处理工具箱的模块化设计(Hermann等人，J.Comput)。化学。2016、37、1511)。将该方法应用于不同分子体系的超快电荷迁移过程，证明了该方法的广泛适用性。研究了N电子动力学关于电子结构、理论水平和基组大小的收敛问题。这提供了对可以对电荷迁移模拟中观察到的动态特征做出的定性和定量陈述的稳健性的评估。©2017威利期刊公司。
The aim of the present contribution is to provide a framework for analyzing and visualizing the correlated many‐electron dynamics of molecular systems, where an explicitly time‐dependent electronic wave packet is represented as a linear combination of N‐electron wave functions. The central quantity of interest is the electronic flux density, which contains all information about the transient electronic density, the associated phase, and their temporal evolution. It is computed from the associated one‐electron operator by reducing the multideterminantal, many‐electron wave packet using the Slater‐Condon rules. Here, we introduce a general tool for post‐processing multideterminant configuration‐interaction wave functions obtained at various levels of theory. It is tailored to extract directly the data from the output of standard quantum chemistry packages using atom‐centered Gaussian‐type basis functions. The procedure is implemented in the open‐source Python program detCI@ORBKIT, which shares and builds on the modular design of our recently published post‐processing toolbox (Hermann et al., J. Comput. Chem. 2016, 37, 1511). The new procedure is applied to ultrafast charge migration processes in different molecular systems, demonstrating its broad applicability. Convergence of the N‐electron dynamics with respect to the electronic structure theory level and basis set size is investigated. This provides an assessment of the robustness of qualitative and quantitative statements that can be made concerning dynamical features observed in charge migration simulations. © 2017 Wiley Periodicals, Inc.