We report the first measurements on the dynamical response of alkanethiol/gold monolayers using a depth-selective tethered probe molecule technique, where 5% of the monolayer is comprised of the probe. Our transient spectroscopic data indicate that, for the first similar to 10 CH2 groups above the gold surface, the local environment is highly rigid, and from these same data, we recover an average tilt angle of 26 degrees, in exact agreement with steady state measurements.