Optical fields interacting with solids
excite single particle quantum
transitions and elicit collective screening responses that define
their penetration, absorption, and reflection. The interplay of these
interactions on the attosecond time scale defines how optical energy
transforms to electronic, setting the limits of efficiency for processes
such as solar energy harvesting or photocatalysis. Our understanding
of light–matter interactions is primarily based on specifying
the electronic structure of solids and initial particles or fields
occupying well-defined states, and the outcome of their interaction
culminating in photoelectron or photon emission and analysis, with
scant ability to follow the transitional, ultrafast many-body interactions
that define it. The optical properties of metals transubstantiate
from metallic to dielectric when the real part of their dielectric
response function, Re[ε(ω)], passes through zero: at low
frequencies, Re[ε(ω)] < 0, and the collective free
electron plasmonic response confers high reflectivity; at high frequencies,
Re[ε(ω)] > 0, and the fields penetrate as charge-density
or longitudinal plasmon waves. How such collective plasmonic responses
decay on the femtosecond time scale into single particle excitations
is cardinal to plasmonics, but not sufficiently well described by
experiment or theory. We examine the spectroscopic signatures of the
nonlinear single particle and collective excitations of the low index
crystals of silver by nonlinear two-photon photoemission spectroscopy,
at frequencies where the bulk dielectric response passes through zero.
We find that the transition through zero dielectric region is reflected
in the nonlinear photoemission spectra, and in particular, the bulk
plasmons decay by giving rise to a non-Einsteinian plasmonic photoemission
component. This response, where the energy of photoelectrons is not
defined by the incoming photons, occurs when photons excite the longitudinal
plasmons, which then decay by exciting photoelectrons selectively
from the Fermi level. Such mode of plasmon decay into hot electrons
is contrary to the general agreement, but confirms a theoretical prediction
by J. J. Hopfield from 1965. Our experiment illuminates a more energy
efficient optical-to-electronic energy flow in metals that so far
has escaped scrutiny.