This paper presents the nonadiabatic molecular dynamics simulation in the solution phase using the spin-flip time-dependent density functional theory (SF-TDDFT). Despite the single-reference level of theory, the SF-TDDFT method can generate the correct topology of S0/S1 crossing points, thus providing a natural S1 → S0 nonadiabatic transition. We extend the gas-phase trajectory surface hopping simulation with the SF-TDDFT [N. Minezawa and T. Nakajima, J. Chem. Phys. 150, 204120 (2019)] to the hybrid quantum mechanical/molecular mechanics (QM/MM) scheme. To this end, we modify the code to evaluate the electrostatic interaction between the QM and MM atoms and to extract the classical MM energy and forces from the MM program package. We apply the proposed method to the photoisomerization reaction of aqueous E-azomethane and anionic green fluorescent protein chromophore in water and compare the results with those of the previous simulation studies based on the multireference methods.

中文翻译：

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利用自旋翻转时间相关的密度泛函理论模拟量子力学/分子机械轨迹的表面跳跃分子动力学。

本文介绍了使用自旋翻转时间相关密度泛函理论（SF-TDDFT）的固相非绝热分子动力学模拟。尽管理论上具有单一参考水平，但SF-TDDFT方法可以生成S0 / S1交叉点的正确拓扑，从而提供自然的S1→S0非绝热转变。我们用SF-TDDFT扩展了气相轨迹表面跳变模拟[N。Minezawa和T. Nakajima，化学杂志。物理 150，204120（2019）]引入混合量子力学/分子力学（QM / MM）方案。为此，我们修改代码以评估QM和MM原子之间的静电相互作用，并从MM程序包中提取经典的MM能量和力。