Origin of discrepancies in inelastic electron tunneling spectra of molecular junctions

We report inelastic electron tunneling spectroscopy (IETS) of multilayer molecular junctions with and without incorporated metal nanoparticles. The incorporation of metal nanoparticles into our devices leads to enhanced IET intensity and a modified line shape for some vibrational modes. The enhancement and line-shape modification are both the result of a low lying hybrid metal nanoparticle-molecule electronic level. These observations explain the apparent discrepancy between earlier IETS measurements of alkane thiolate junctions by Kushmerick et al. [Nano Lett. 4, 639 (2004)] and Wang et al. [Nano Lett. 4, 643 (2004)].