Pure and Applied Chemistry

Abstract: Photon-initiated shape transformation of n-alkanethiol-derivatized noble metal nanoparticles has been studied with variations of metal, alkanethiol, and solvent. Silver nanoparticles undergo fragmentation upon irradiation while gold ones barely do. Silver/gold composite particles follow the case of silver with a reduced efficiency. The efficiency decreases as alkanethiol length or solvent dipole moment increases. Following the conduction of thermalized photon energy, alkanethiol can dissociate in a period of heat dissipation, and some of dethiolated particles fragment within the recombination time. Prior to the thermal conduction, shape transformation via melt and vaporization also occurs for both metals but this effect is less apparent for silver because of more notable fragmentation followed. The difference in the transformation of two metals is ascribed to the differences in work function, oxidation potential, atomization enthalpy, and particle size. Smaller fragmentation efficiency with more polar solvent or longer alkanethiol is attributed mainly to relatively smaller dissociation rate compared with heat dissipation rate.