Understanding
the physics of surface plasmons and related phenomena requires knowledge
of the spatial, temporal, and spectral distributions of the total
electromagnetic field excited within nanostructures and their interfaces,
which reflects the electromagnetic mode excitation, confinement, propagation,
and damping. We present a microscopic and spectroscopic study of the
plasmonic response in single-crystalline Ag wires grown in
situ on Si(001) substrates. Excitation of the plasmonic modes
with broadly tunable (UV–IR) femtosecond laser pulses excites
ultrafast multiphoton photoemission, whose spatial distribution is
imaged with an aberration-corrected photoemission electron microscope,
thereby providing a time-integrated map of the locally enhanced electromagnetic
fields. We show by tuning the wavelength, polarization, and k-vector of the incident laser light that for a few micrometers
long wires we can selectively excite either the propagating surface
plasmon polariton modes or high-order multipolar resonances of the
Ag/vacuum and Ag/Si interfaces. Moreover, upon tuning the excitation
wavelength from the UV to the near-IR spectral regions, we find that
the resonant plasmonic modes shift from the top of the wires to selvedge
at the Ag/Si interface. Our results, supported by numerical simulations,
provide a better understanding of the optical response of metal/semiconductor
structures and guidance toward the design of polaritonic and nanophotonic
devices with enhanced properties, as well as suggest mechanisms for
plasmonically enhanced photocatalysis.