Spectral Diffusion of Excitons in 3,4,9,10-Perylenetetracarboxylic-diimide (PTCDI) Thin Films.

In this work, we study spectral diffusion of molecular excitons in thin films of 3,4,9,10-perylenetetracarboxylic-diimide by using two-dimensional electronic spectroscopy (2DES). Temperature dependence of the spectral diffusion is studied from 105 to 471 K by analyzing the center line slope (CLS) of the ground-state bleach in the 2DES signal. A significant acceleration of the decay of the CLS with increasing the temperature is observed, which cannot be explained by a linear system-bath coupling model with a harmonic bath. We propose an anharmonic coupling model as the underlying mechanism, in which the exciton energy gap fluctuations by a high-frequency intramolecular vibration are enhanced by coupling with a low-frequency phonon mode.