Institute of Physics, Faculty of Mathematics and Physics, Charles University, Ke Karlovu 5, Prague 121 16, Czech Republic.
J Chem Phys. 2017 Aug 28;147(8):084104. doi: 10.1063/1.4999680.
We present a computational model for the spectra of molecular aggregates with signatures of vibronic progression. Vibronic dynamics is implemented by coupling the dynamics of Frenkel excitons with underdamped vibrations. Vibrational dynamics includes linear damping resulting in the exponential decay and quadratic damping inducing subexponential or power law relaxation and increasing vibrational decoherence as demonstrated on lineshapes of the absorption spectrum. Simulations of the third-order coherent response account for bath reorganization during excitonic transport, which allows us to study the line-shape evolution of cross peaks of 2D spectra.
我们提出了一个具有振子进动特征的分子聚集体光谱的计算模型。通过将弗伦克尔激子的动力学与欠阻尼振动耦合，实现了振子动力学。振动动力学包括线性阻尼，导致指数衰减和二次阻尼诱导亚指数或幂律松弛，并增加振动退相干，如吸收光谱的线形状所示。三阶相干响应的模拟考虑了激子输运过程中的溶剂重组，这使我们能够研究 2D 光谱的交叉峰的线形状演化。
