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Journal of Chemical Physics, Vol.106, No.15, 6217-6221, 1997
Photoabsorption and Ionization Energies of Nonstoichiometric CsI Clusters - Metallization of a Salt
Cs and CsI vapors were mixed to produce clusters having compositions varying from pure metal to the ionic salt. Ionization potential measurements on these clusters were performed using photoionization and a time-of-flight mass spectrometer. Results are reported for two metallization sequences, Cs14In for n = 1 - 13 and CsmIn for m + n = 26, 27 and m>n. The ionization potentials show a good qualitative agreement with recent computations and experiments carried out on nonstoichiometric NaF. Photoabsorption spectra are presented for CsmIn clusters for m + n =26, 27. The spectra were obtained by heating mass selected clusters in a beam by means of photoabsorption to induce evaporation of atoms. The resulting mass loss was observed in a time-of-flight mass spectrometer. The spectra of metal rich clusters with m - n > 8 are very similar, showing one broad absorption peak around 1.42 eV, the energy of the plasmon resonance of pure Cs clusters of this size. CsmIn+ clusters with less than 7 excess valence electrons show a clear peak splitting. The shape and width of the peaks is not consistent with the picture of a homogeneous metallic cluster. In this range, a "demetallization" seems to take place.
Keywords:ALKALI-HALIDE CLUSTERS;SODIUM CLUSTERS;MELTING TEMPERATURE;METAL-CLUSTERS;EXCITED-STATES;SPECTROSCOPY;RESONANCE;IONS