Photoelectron spectra of aluminum cluster anions: Temperature effects andab initiosimulations

Photoelectron (PES) spectra from aluminum cluster anions, Alₙ^- $(12<~n<~15),$ at various temperature regimes, were studied using ab initio molecular dynamics simulations and experimentally. The calculated PES spectra, obtained via shifting of the simulated electronic densities of states by the self-consistently determined values of the asymptotic exchange-correlation potential, agree well with the measured ones, allowing reliable structural assignments and theoretical estimation of the clusters' temperatures.