A comparison of photoelectron spectroscopy and two-photon ionization spectroscopy: Excited states of Au2, Au3, and Au4

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Abstract
Photoelectron spectra of Au−n with n=2–4 are reported. Due to the relatively high photon energy used in our experiment (hν=6.424 eV) and the energy resolution of about 50 meV, various transitions into excited states of the neutral clusters are resolved. It is demonstrated that photoelectron spectra can serve as a map of the electronic states of a cluster, while the high resolution of the resonant two-photon ionization (R2PI) method gains information about the symmetry of the states. The comparison with similar data of Ag−n clusters indicates the influence of relativistic effects and the large spin–orbit splitting for Au.