RESUMO
Structurally well-defined graphene nanoribbons (GNRs) are nanostructures with unique optoelectronic properties. In the liquid phase, strong aggregation typically hampers the assessment of their intrinsic properties. Recently we reported a novel type of GNRs, decorated with aliphatic side chains, yielding dispersions consisting mostly of isolated GNRs. Here we employ two-dimensional electronic spectroscopy to unravel the optical properties of isolated GNRs and disentangle the transitions underlying their broad and rather featureless absorption band. We observe that vibronic coupling, typically neglected in modeling, plays a dominant role in the optical properties of GNRs. Moreover, a strong environmental effect is revealed by a large inhomogeneous broadening of the electronic transitions. Finally, we also show that the photoexcited bright state decays, on the 150 fs time scale, to a dark state which is in thermal equilibrium with the bright state, that remains responsible for the emission on nanosecond time scales.
RESUMO
Vibrational coherences in ultrafast pump-probe (PP) and 2D electronic spectroscopy (2DES) provide insights into the excited state dynamics of molecules. Femtosecond coherence spectra and 2D beat maps yield information about displacements of excited state surfaces for key vibrational modes. Half-broadband 2DES uses a PP configuration with a white light continuum probe to extend the detection range and resolve vibrational coherences in the excited state absorption (ESA). However, the interpretation of these spectra is difficult as they are strongly dependent on the spectrum of the pump laser and the relative displacement of the excited states along the vibrational coordinates. We demonstrate the impact of these convoluting factors for a model based upon cresyl violet. A careful consideration of the position of the pump spectrum can be a powerful tool in resolving the ESA coherences to gain insights into excited state displacements. This paper also highlights the need for caution in considering the spectral window of the pulse when interpreting these spectra.
RESUMO
Knowledge of relative displacements between potential energy surfaces (PES) is critical in spectroscopy and photochemistry. Information on displacements is encoded in vibrational coherences. Here we apply ultrafast two-dimensional electronic spectroscopy in a pump-probe half-broadband (HB2DES) geometry to probe the ground- and excited-state potential landscapes of cresyl violet. 2D coherence maps reveal that while the coherence amplitude of the dominant 585 cm-1 Raman-active mode is mainly localized in the ground-state bleach and stimulated emission regions, a 338 cm-1 mode is enhanced in excited-state absorption. Modeling these data with a three-level displaced harmonic oscillator model using the hierarchical equation of motion-phase matching approach (HEOM-PMA) shows that the S1 â S0 PES displacement is greater along the 585 cm-1 coordinate than the 338 cm-1 coordinate, while Sn â S1 displacements are similar along both coordinates. HB2DES is thus a powerful tool for exploiting nuclear wavepackets to extract quantitative multidimensional, vibrational coordinate information across multiple PESs.