Pyridine layers on Cu(110) possess a strong electric field due to the large dipole of adsorbed pyridine. This electric field is visible as an enhanced sum frequency response from both the copper surface electrons and the aromatic C-H stretch of pyridine via a third order susceptibility. In response to a visible pump pulse, both surface electron and C-H stretch sum frequency signals are reduced on a subpicosecond time scale. In addition, the relative phase between the two signals changes over a few hundred femtoseconds, which indicates a change in the electronic structure of the adsorbate. We explain the transients as a consequence of the previously observed pyridine dipole field reversal when the pump pulse excites electrons into the pyridine π* orbital. The pyridine anions in the pyridine layer cause a large-scale structural change which alters the pyridine-copper bond, reflected in the altered sum frequency response.