Radiative Enhancement of Linear and Third-Order Vibrational Excitations by an Array of Infrared Plasmonic Antennas

Infrared gold antennas localize enhanced near fields close to the metal surface, when excited at the frequency of their plasmon resonance, and amplify vibrational signals from the nearby molecules. We study the dependence of the signal enhancement on the thickness of a polymer film containing vibrational chromophores, deposited on the antenna array, using linear (FTIR) and third-order femtosecond vibrational spectroscopy (transient absorption and 2DIR). Our results show that for a film thickness beyond only a few nanometers the near-field interaction is not sufficient to account for the magnitude of the observed signal, which nevertheless has a clear Fano line shape, suggesting a radiative origin of the molecule–plasmon interaction. The mutual radiative damping of plasmonic and molecular transitions leads to the spectroscopic signal of a molecular vibrational excitation to be enhanced by up to a factor of 50 in the case of linear spectroscopy and over 2000 in the case of third-order spectroscopy. A qualitative explanation for the observed effect is given by the extended coupled oscillators model, which takes into account both near-field and radiative interactions between the plasmonic and molecular transitions

Band-Selective Ballistic Energy Transport in Alkane Oligomers: Toward Controlling the Transport Speed

Intramolecular transport of vibrational energy in two series of oligomers featuring alkane chains of various length was studied by relaxation-assisted two-dimensional infrared spectroscopy. The transport was initiated by exciting various end-group modes (tags) such as different modes of the azido (ν­(NN) and ν­(NN)), carboxylic acid (ν­(CO)), and succinimide ester (ν_as(CO)) with short mid-IR laser pulses. It is shown that the transport via alkane chains is ballistic and the transport speed is dependent on the type of the tag mode that initiates the transport. The transport speed of 8.0 Å/ps was observed when initiated by either ν­(CO) or ν_as(CO). When initiated by ν­(NN) and ν­(NN), the transport speed of 14.4 ± 2 and 11 ± 4 Å/ps was observed. Analysis of the vibrational relaxation channels of different tags, combined with the results for the group velocity evaluation, permits identification of the chain bands predominantly contributing to the transport for different cases of the transport initiation. For the transport initiated by ν­(NN) the CH₂ twisting and wagging chain bands were identified as the major energy transport channels. For the transport initiated by ν­(CO), the C–C stretching and CH₂ rocking chain bands served as major energy transporters. The transport initiated by ν­(NN) results in direct formation of the wave packet within the CH₂ twisting and wagging chain bands. These developments can aid in designing molecular systems featuring faster and more controllable energy transport in molecules