Charge Transfer-Mediated Dramatic Enhancement of Raman Scattering upon Molecular Point Contact Formation.

Charge-transfer enhancement of Raman scattering plays a crucial role in current-carrying molecular junctions. However, the microscopic mechanism of light scattering in such nonequilibrium systems is still imperfectly understood. Here, using low-temperature tip-enhanced Raman spectroscopy (TERS), we investigate how Raman scattering evolves as a function of the gap distance in the single C60-molecule junction consisting of an Ag tip and various metal surfaces. Precise gap-distance control allows the examination of two distinct transport regimes, namely tunneling regime and molecular point contact (MPC). Simultaneous measurement of TERS and the electric current in scanning tunneling microscopy shows that the MPC formation results in dramatic Raman enhancement that enables one to observe the vibrations undetectable in the tunneling regime. This enhancement is found to commonly occur not only for coinage but also transition metal substrates. We suggest that the characteristic enhancement upon the MPC formation is rationalized by charge-transfer excitation.

First-Principles Simulations of Tip Enhanced Raman Scattering Reveal Active Role of Substrate on High-Resolution Images.

Tip-enhanced Raman scattering (TERS) has emerged as a powerful tool to obtain subnanometer spatial resolution fingerprints of atomic motion. Theoretical calculations that can simulate the Raman scattering process and provide an unambiguous interpretation of TERS images often rely on crude approximations of the local electric field. In this work, we present a novel and first-principles-based method to compute TERS images by combining Time Dependent Density Functional Theory (TD-DFT) and Density Functional Perturbation Theory (DFPT) to calculate Raman cross sections with realistic local fields. We present TERS results on free-standing benzene and C60 molecules, and on the TCNE molecule adsorbed on Ag(100). We demonstrate that chemical effects on chemisorbed molecules, often ignored in TERS simulations of larger systems, dramatically change the TERS images. This observation calls for the inclusion of chemical effects for predictive theory-experiment comparisons and an understanding of molecular motion at the nanoscale.