Malý Pavel, Somsen Oscar J G, Novoderezhkin Vladimir I, Mančal Tomáš, van Grondelle Rienk
Department of Physics and Astronomy, Vrije Universiteit Amsterdam, De Boelelaan 1081, 1081 HV, Amsterdam, The Netherlands.
Institute of Physics, Charles University in Prague, Ke Karlovu 5, 12116, Prague, Czech Republic.
Chemphyschem. 2016 May 4;17(9):1356-68. doi: 10.1002/cphc.201500965. Epub 2016 Mar 22.
Nuclear vibrations play a prominent role in the spectroscopy and dynamics of electronic systems. As recent experimental and theoretical studies suggest, this may be even more so when vibrational frequencies are resonant with transitions between the electronic states. Herein, a vibronic multilevel Redfield model is reported for excitonically coupled electronic two-level systems with a few explicitly included vibrational modes and interacting with a phonon bath. With numerical simulations the effects of the quantized vibrations on the dynamics of energy transfer and coherence in a model dimer are illustrated. The resonance between the vibrational frequency and energy gap between the sites leads to a large delocalization of vibronic states, which then results in faster energy transfer and longer-lived mixed coherences.
核振动在电子系统的光谱学和动力学中起着重要作用。正如最近的实验和理论研究所表明的，当振动频率与电子态之间的跃迁共振时，情况可能更是如此。在此，我们报道了一种振动电子多能级雷德菲尔德模型，用于具有几个明确包含的振动模式并与声子浴相互作用的激子耦合电子双能级系统。通过数值模拟，说明了量子化振动对模型二聚体中能量转移和相干动力学的影响。振动频率与位点之间的能隙共振导致振动电子态的大量离域，进而导致更快的能量转移和更长寿命的混合相干。
