Intermolecular Forces Dictate Vibrational Energy Transfer in Plasmonic-Molecule Systems.

Plasmonic materials are a promising category of photocatalysts for solar energy harvesting and conversion. However, there are some significant obstacles that need to be overcome to make plasmonic catalysts commercially available. One major challenge is to obtain a systematic understanding of how to design and optimize plasmonic systems from the perspective of both plasmonic materials and reagent molecules to achieve highly efficient and selective catalysis. It is well-known that the contributions of plasmon-molecule interactions such as plasmon-induced resonant energy transfer and charge transfer to the catalytic mechanism are rather complicated and possibly multifold. Observation of these phenomena is challenging due to the highly heterogeneous nature of plasmonic substrates as well as the large difference in sizes and optical cross sections between plasmonic materials and molecules. In this work, we use a molecular perspective to examine the crucial process of energy transfer between plasmons and molecules, with the goal of determining which experimental parameters can be used to control this energy flow. We employ ultrafast surface-enhanced anti-Stokes and Stokes Raman spectroscopy to investigate vibrational energy transfer in plasmonic-molecule systems. By comparing the energy transfer kinetics of five different aromatic thiols on the picosecond time scale, we find that intermolecular forces play an important role in energy distribution in molecules adsorbed to plasmonic materials, which changes the amount of energy deposited onto the molecule and the lifetime of the energy deposited. Our work implies that careful consideration of catalyst loading and molecule adsorption geometry is crucial for enhancing or suppressing the rate and efficiency of plasmon-driven energy transfer.