Effects of Hydrostatic Pressure on the Surface Plasmon Resonance of Gold Nanocrystals.

Abstract

The surface plasmon resonances of gold nanospheres and nanorods have been measured as a function of hydrostatic pressure up to 17 GPa in methanol-ethanol 4:1 solvent and up to 10 GPa in paraffin. Both the sphere resonance and the longitudinal rod resonance exhibit redshifts, whereas the transverse rod mode shows an extremely weak redshift or blueshift depending on the nanorod aspect ratio. Solidification of the solvent around 11 GPa causes some aggregation of the particles, readily identified through broadening of the surface plasmon band and further redshifting. Spectra collected during loading and unloading cycles exhibit only minimal hysteresis if the pressure remains below 11 GPa. The surface plasmon shifts are the result of two competing effects. Compression of the conduction electrons in the metals increases the bulk plasma frequency, which causes a blueshift. However, the increase in the solvent density under hydrostatic load leads to an increase in the solvent refractive index, which in turn leads to a redshift. We find that after accounting for the solvent contribution, we can spectroscopically determine the bulk modulus of the gold nanoparticles with a precision of 10%. The value obtained of K0 = 190 GPa is significantly higher than the value for bulk gold (167 GPa). Furthermore, we show that pressure-induced solidification causes a significant broadening and anomalous shift of the surface plasmon band that we attribute to aggregation and nanorod deformation.