Plasmon extinguishment by bandedge shift identified as a second-order spectroscopic differentiation

Optical excitation of metallic nanostructures induces strong intraband transitions, leaving transient depletion below the Fermi level, which allows transient interband transition to this depletion band. This is equivalent to the lowering of the threshold for interband transitions and pushes the plasmonic band to the red. As a result, localized surface plasmon resonance (LSPR) is “extinguished” or “quenched” around the bandedge, in contrast, the interband optical absorption becomes enhanced and redshifted. The corresponding transient absorption (TA) signals have equal lifetimes and opposite signs. Moreover, the TA spectrum is found to be a second-order differential of the steady-state optical extinction spectrum over the studied band. This is a commonly existing mechanism for metallic nanostructures and verified with gold in this work. Such a discovery is completely different from the optical-excitation-induced redshift of LSPR through enhanced electronic scattering and is important for understanding the ultrafast spectroscopic response of plasmonic nanostructures with clear photophysical insights, supplying solid basis for exploring optical logic device and optical data processing techniques.