使用含时密度矩阵重正化群高效模拟实时分子电子动力学
Simulating real-time molecular electron dynamics efficiently using the time-dependent density matrix renormalization group
AI总结：
该研究探讨了含时密度矩阵重正化群（TDDMRG）模拟参数的收敛行为，提出了优化动力学的轨道选择方法，并成功应用于糠醛电荷迁移动力学，揭示了亚飞秒时间尺度的电离态转换。
摘要：
与基态电子结构优化相比，分子实时电子动力学的精确模拟通常要困难得多。为了模拟电子动力学，含时密度矩阵重正化群（TDDMRG）已被证明能在准确性和成本之间提供有吸引力的折中方案。然而，许多模拟参数会显著影响TDDMRG模拟的质量和效率。到目前为止，尚不清楚基态DMRG的常规经验是否适用于TDDMRG，并且缺乏如何选择这些参数的指导原则。在此，为了建立这样的指导原则，我们研究了主要TDDMRG模拟参数的收敛行为，例如时间积分器、轨道的选择，以及针对复值非单重态的矩阵乘积态表示的选择。此外，我们提出了一种选择专门用于优化动力学的轨道的方法。最后，我们通过将TDDMRG应用于糠醛中的电荷迁移电离动力学来展示其能力，其中我们揭示了在不到一飞秒的时间内，从具有$σ$特征的电离态到具有$π$特征的电离态的快速转换。
英文摘要：
Compared to ground state electronic structure optimizations, accurate simulations of molecular real-time electron dynamics are usually much more difficult to perform. To simulate electron dynamics, the time-dependent density matrix renormalization group (TDDMRG) has been shown to offer an attractive compromise between accuracy and cost. However, many simulation parameters significantly affect the quality and efficiency of a TDDMRG simulation. So far, it is unclear whether common wisdom from ground state DMRG carries over to the TDDMRG, and a guideline on how to choose these parameters is missing. Here, in order to establish such a guideline, we investigate the convergence behavior of the main TDDMRG simulation parameters, such as time integrator, the choice of orbitals, and the choice of matrix-product-state representation for complex-valued non-singlet states. In addition, we propose a method to select orbitals that are tailored to optimize the dynamics. Lastly, we showcase the TDDMRG by applying it to charge migration ionization dynamics in furfural, where we reveal a rapid conversion from an ionized state with a $σ$ character to one with a $π$ character within less than a femtosecond.
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