Photoionization measurements on Al·ArN clusters (N < 150) in a cold cluster beam have been used to determine ionization threshold energies El, th(N) of the metal atom in a variable-size dielectric medium. The El,th(N) values descend from the atomic value [5.99 eV (1 eV ≈ 1.602 × 10-19 J)] to below 5.5 eV near N ≈ 55. The El, th(N) functional form is compared to dielectric continuum predictions and to N-specific Monte Carlo calculations incorporating polarization and model-potential interactions. Satisfactory agreement is obtained when a strong neutral Al-Ar interaction is assumed. Measurements of the slow fragmentation probability indicate that near-threshold ionization of smaller clusters (N < 25) produces negligible fragmentation, resulting in N-specific threshold measurements. Comparison of neutral cluster distributions, measured by threshold photoionization to the corresponding cold Al+·ArN distribution (produced in the source) supports a predominant charge-invariance of the icosahedral-based structures, also found in Monte Carlo simulations. By contrast, photo-absorption spectra in bound states, as exemplified by R2PI spectra of the Al 3p → 4s transition, exhibit only a small fraction (ca. 0.12 eV) of the bulk shift (ca. 0.6 eV). This result may be partly explicable in terms of the distinction between sudden and adiabatic polarization energies in the two experiments.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry