Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie, Université Pierre et Marie Curie - Sorbonne Universités, Paris, France.
CNR-NANO Institute of Nanoscience, Modena, Italy.
J Chem Phys. 2017 Feb 14;146(6):064116. doi: 10.1063/1.4975620.
The dynamics of the electrons for a molecule in solution is coupled to the dynamics of its polarizable environment, i.e., the solvent. To theoretically investigate such electronic dynamics, we have recently developed equations of motion (EOM) for the apparent solvent polarization charges that generate the reaction field in the Polarizable Continuum Model (PCM) for solvation and we have coupled them to a real-time time-dependent density functional theory (RT TDDFT) description of the solute [S. Corni et al., J. Phys. Chem. A 119, 5405 (2014)]. Here we present an extension of the EOM-PCM approach to a Time-Dependent Configuration Interaction (TD CI) description of the solute dynamics, which is free from the qualitative artifacts of RT TDDFT in the adiabatic approximation. As tests of the developed approach, we investigate the solvent Debye relaxation after an electronic excitation of the solute obtained either by a π pulse of light or by assuming the idealized sudden promotion to the excited state. Moreover, we present EOM for the Onsager solvation model and we compare the results with PCM. The developed approach provides qualitatively correct real-time evolutions and is promising as a general tool to investigate the electron dynamics elicited by external electromagnetic fields for molecules in solution.
溶液中分子的电子动力学与可极化环境（即溶剂）的动力学耦合。为了从理论上研究这种电子动力学，我们最近开发了用于溶剂化的极化连续体模型 (PCM) 中反应场的表观溶剂极化电荷的运动方程 (EOM)，并将其与溶质的实时含时密度泛函理论 (RT TDDFT) 描述耦合[ S. Corni 等人，J. Phys. Chem. A 119, 5405 (2014)]。在这里，我们将 EOM-PCM 方法扩展到溶质动力学的含时组态相互作用 (TD CI) 描述，该方法在绝热近似下避免了 RT TDDFT 的定性伪像。作为所开发方法的测试，我们研究了溶质电子激发后溶剂的德拜弛豫，该激发是通过光的π脉冲获得的，或者假设理想的激发态跃迁。此外，我们还提出了 Onsager 溶剂化模型的 EOM，并将结果与 PCM 进行了比较。所开发的方法提供了定性正确的实时演化，有望成为研究溶液中分子在外加电磁场下引发的电子动力学的通用工具。
