Menzel Jan Paul, de Groot Huub J M, Buda Francesco
Leiden Institute of Chemistry , Leiden University , PO Box 9502, 2300 RA Leiden , The Netherlands.
J Phys Chem Lett. 2019 Nov 7;10(21):6504-6511. doi: 10.1021/acs.jpclett.9b02408. Epub 2019 Oct 11.
Electron-nuclear (vibronic) coupling has emerged as an important factor in determining the efficiency of energy transfer and charge separation in natural and artificial photosynthetic systems. Here we investigate the photoinduced charge-transfer process in a hydrogen-bonded donor-acceptor molecular complex. By using real-time quantum-classical simulations based on time-dependent Kohn-Sham equations, we follow in detail the relaxation from the Franck-Condon point to the region of strong nonadiabatic coupling where electron transfer occurs. We elucidate how the charge transfer is coupled to specific vibrational modes and how it is affected by isotope substitution. The importance of resonance in nuclear and electron dynamics and the role of dynamic symmetry breaking are emphasized. Using the dipole moment as a descriptive parameter, exchange of angular momentum between nuclear and electronic subsystems in an electron-nuclear resonant process is inferred. The performed simulations support a nonadiabatic conversion via adiabatic passage process that was recently put forward. These results are relevant in deriving rational design principles for solar-to-fuel conversion devices.
电子 - 核（振转）耦合已成为决定天然和人工光合系统中能量转移和电荷分离效率的一个重要因素。在此，我们研究了一个氢键供体 - 受体分子复合物中的光诱导电荷转移过程。通过基于含时Kohn - Sham方程的实时量子 - 经典模拟，我们详细追踪了从弗兰克 - 康登点到发生电子转移的强非绝热耦合区域的弛豫过程。我们阐明了电荷转移如何与特定振动模式耦合以及它如何受到同位素取代的影响。强调了核与电子动力学中共振的重要性以及动态对称性破缺的作用。利用偶极矩作为描述参数，推断了电子 - 核共振过程中核与电子子系统之间角动量的交换。所进行的模拟支持了最近提出的通过绝热通道过程的非绝热转换。这些结果对于推导太阳能 - 燃料转换装置的合理设计原则具有重要意义。
