Picosecond Dynamics of Colloidal Gold Nanoparticles

Abstract

Colloidal gold nanoparticles with an average radius of 15 nm have a surface plasmon absorption band at 530 nm. Excitation by laser pulses of 450 fs duration, and wavelength of 600 or 380 nm “bleached” the plasmon band and produced a transient absorption at the wings of the “bleach” spectrum. The transient absorption was found to have a similar temporal behavior at different wavelengths. Analysis of their temporal behavior showed two time constants: 2.5 ps, and a slower component of >50 ps. Laser excitation close to the plasmon band at 600 nm leads to the formation of “hot” non-Fermi electronic distribution within the colloidal particles. Transient absorption from these “hot” electrons led to different absorptions from that of the plasmon absorption of “cold” electrons. The “hot” electrons relax via electron−phonon coupling in 2.5 ps, and the phonon−phonon relaxation of the lattice occurs in >50 ps. At 380 nm excitation, the amplitude of the blue wing becomes smaller, and the slow component becomes longer, which could be due to possible excitation of the d-band electrons. These results are discussed in terms of Mie theory and a two-temperature model (TTM), and their consequences on the optical absorption spectrum.