Theory of multiphoton photoemission disclosing excited states in conduction band of individual TiO_(2) nanoparticles

A theory of multiphoton photoemission is derived to explain the experimentally observed monotonic decrease with the wavelength in the electron yield of TiO_(2) nanoparticles(NPs)by as large as four orders of magnitude.It is found that the fitting parameter corresponds to the energy position of Ti3d e_(g) and t_(2g) states,and the derived theory is a novel diagnostic of excited states in the conduction band,very importantly,applicable to individual NPs.The difference between four-photon slope NPs and three-photon slope NPs is attributed to the difference in defect density.The success of the theory in solving the puzzling result shows that thermal emission from high-lying levels may dominate over direct multiphoton ionization in solids when the photon number larger than four is required.