Disentangling Light- and Temperature-Induced Thermal Effects in Colloidal Au Nanoparticles.

We present temperature-dependent (from room temperature to 80 °C) absorption spectra of Au/SiO core-shell nanoparticles (NPs) (core diameter: ∼25 nm) in water in the range from 1.5 to 4.5 eV, which spans the localized surface plasmon resonance (LSPR) and the interband transitions. A decrease in absorption with temperature over the entire spectral range is observed, which is more prominent at the LSPR. These changes are well reproduced by theoretical calculations of the absorption spectra, based on the experimentally measured temperature-dependent real (ε) and imaginary (ε) parts of the dielectric constant of Au NPs and of the surrounding medium. In addition, we model the photoinduced response of the NPs over the entire spectral range. The experimental and theoretical results of the thermal heating and the simulations of the photoinduced heating are compared with the ultrafast photoinduced transient absorption (TA) spectra upon excitation of the LSPR. These show that while the latter is a reliable monitor of heating of the NP and its environment, the interband region mildly responds to heating but predominantly to the population evolution of charge carriers.