Ultrafast Time-Domain Spectroscopy Reveals Coherent Vibronic Couplings upon Electronic Excitation in Crystalline Organic Thin Films

The coherent coupling between electronic excitations and vibrational modes of molecules largely affects the optical and charge transport properties of organic semiconductors and molecular solids. To analyze these couplings by means of ultrafast spectroscopy, highly ordered crystalline films with large domains are particularly suitable because the domains can be addressed individually, hence allowing azimuthal polarization-resolved measurements. Impressive examples of this are highly ordered crystalline thin films of perfluoropentacene (PFP) molecules, which adopt different molecular orientations on different alkali halide substrates. Here, we report polarization-resolved time-domain vibrational spectroscopy with 10 fs time resolution and Raman spectroscopy of crystalline PFP thin films grown on NaF(100) and KCl(100) substrates. Coherent oscillations in the time-resolved spectra reveal vibronic coupling to a high-frequency, 25 fs, in-plane deformation mode that is insensitive to the optical polarization, while the coupling to a lower-frequency, 85 fs, out-of-plane ring bending mode depends significantly on the crystalline and molecular orientation. Comparison with calculated Raman spectra of isolated PFP molecules in vacuo supports this interpretation and indicates a dominant role of solid-state effects in the vibronic properties of these materials. Our results represent a first step toward uncovering the role of anisotropic vibronic couplings for singlet fission processes in crystalline molecular thin films.