The multiphoton excitation pathways of plasmonic nanorod assemblies are described. By using dolmen structures formed from the directed assembly of three gold nanorods, plasmon-mediated three-photon excitation is resolved. These high-order multiphoton excitation channels were accessed by resonantly exciting a hybrid mode of the dolmen structure that was resonant with the 800-nm carrier wavelength of an ultrafast laser system. Rotation of the exciting field polarization to a non-resonant configuration did not generate third-order responses. Hence, the multiphoton excitation and resultant non-equilibrium electron distributions were generated by structure- and mode-selective excitation. Correlation between high-order and resonant plasmon excitation was achieved through sub-cycle time-resolved interferometric detection of incoherent nonlinear emission signals. The results illustrate the advantages of nonlinear optical interferometry and Fourier analysis for distinguishing plasmon-mediated processes from those that do not require plasmon excitation.
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