Temperature-dependent photoionization thresholds of alkali-metal nanoparticles reveal thermal expansion and the melting transition

A precision measurement of the photoionization of pure sodium and potassium nanoparticles isolated in a beam enabled an accurate determination of their work functions as a function of temperature. In addition to resolving and quantifying the initial gradual decrease of the work function with temperature, which is associated with thermal expansion, the experiment revealed that the work function then undergoes a distinct drop both in magnitude and in slope that signifies the onset of nanoparticle melting. This establishes that a structural phase transition can be detected via a high-resolution measurement of the photoemission threshold. The melting temperature of nanoparticles with diameters of 7-9 nm is reduced by nearly 100 K relative to the bulk value. This suppression aligns with predictions from the Gibbs-Thomson equation which describes finite-size phase transitions.