Using an ultrafast nonlinear coherent vibrational spectroscopy technique termed “vibrational sum-frequency generation”, we have studied a number of systems where molecules on metal surfaces undergo profound structural or chemical changes. In this talk I will describe several of these efforts. In one case, the molecules are bound to a metal electrode in a spectroelectrochemical cell, and we have studied the oxidation of CO on Pt surfaces, the reduction of CO2 on Pt and Ag surfaces, and the formation of solid-electrolyte interphases in model lithium-ion batteries. In the second case, molecules are bound to a metal surface that is flash-heated by a short laser pulse, which causes heat to flow from the attachment point through the molecules. This nanoscale heat transport can be probed with high spatial and temporal resolution. In the third case, molecules bound to a metal surface are subjected to a high pressure shock wave which smashes them against a polymer wall. It’s hard on the poor molecules, but this ultrafast compression process can also be probed with a high level of detail.