A scanning tunneling microscope (STM) capable of performing pump-probe spectroscopy integrates unmatched atomic-scale resolution with high temporal resolution. In recent years, the union of electronic, terahertz, or visible/near-infrared pulses with STM has contributed to our understanding of the atomic-scale processes that happen between milliseconds and attoseconds. This time-resolved STM (TR-STM) technique is evolving into an unparalleled approach for exploring the ultrafast nuclear, electronic, or spin dynamics of molecules, low-dimensional structures, and material surfaces. Here, we review the recent advancements in TR-STM; survey its application in measuring the dynamics of three distinct systems, nucleus, electron, and spin; and report the studies on these transient processes in a series of materials. Besides the discussion on state-of-the-art techniques, we also highlight several emerging research topics about the ultrafast processes in nanoscale objects where we anticipate that the TR-STM can help broaden our knowledge.

Direct imaging of single molecules at nanostructured interfaces is a grand challenge with potential to enable new, precise material architectures and technologies. Of particular interest are the structural morphology and spectroscopic signatures of the adsorbed molecule, where modern probes are only now being developed with the necessary spatial and energetic resolution to provide detailed information at the molecule-surface interface. Here, we directly characterize the adsorption of individual m-terphenyl isocyanide ligands on a reconstructed Au(111) surface through scanning tunneling microscopy and inelastic electron tunneling spectroscopy. The site-dependent steric pressure of the various surface features alters the vibrational fingerprints of the m-terphenyl isocyanides, which are characterized with single-molecule precision through joint experimental and theoretical approaches. This study provides molecular-level insights into the steric-pressure-enabled surface binding selectivity as well as its effect on the chemical properties of individual surface-binding ligands.