Center for Computational Molecular Science and Technology, School of Chemistry and Biochemistry, Georgia Institute of Technology, Atlanta, Georgia 30318, USA.
Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, USA.
J Chem Phys. 2019 Nov 7;151(17):171102. doi: 10.1063/1.5126945.
In this work, we present a time-dependent (TD) selected configuration interaction method based on our recently introduced adaptive configuration interaction (ACI). We show that ACI, in either its ground or excited state formalisms, is capable of building a compact basis for use in real-time propagation of wave functions for computing electron dynamics. TD-ACI uses an iteratively selected basis of determinants in real-time propagation capable of capturing strong correlation effects in both ground and excited states, all with an accuracy-and associated cost-tunable by the user. We apply TD-ACI to study attosecond-scale migration of charge following ionization in small molecules. We first compute attosecond charge dynamics in a benzene model to benchmark and understand the utility of TD-ACI with respect to an exact solution. Finally, we use TD-ACI to reproduce experimentally determined ultrafast charge migration dynamics in iodoacetylene. TD-ACI is shown to be a valuable benchmark theory for electron dynamics, and it represents an important step toward accurate and affordable TD multireference methods.
在这项工作中，我们提出了一种基于我们最近引入的自适应组态相互作用（ACI）的时变（TD）选择组态相互作用方法。我们表明，ACI 无论是在其基态还是激发态形式中，都能够构建一个紧凑的基，用于实时传播波函数以计算电子动力学。TD-ACI 使用实时传播中迭代选择的行列式基，能够捕获基态和激发态中的强相关效应，所有这些都可以由用户调整精度和相关成本。我们应用 TD-ACI 研究小分子中电离后电荷的阿秒级迁移。我们首先在苯模型中计算阿秒电荷动力学，以基准和理解 TD-ACI 相对于精确解的实用性。最后，我们使用 TD-ACI 再现碘乙炔中实验确定的超快电荷迁移动力学。TD-ACI 被证明是电子动力学的一个有价值的基准理论，它是朝着准确和经济的 TD 多参考方法迈出的重要一步。
