Structural determination of neutral Con clusters (n = 4–10,13) through IR–UV two-color vibrational spectroscopy and DFT calculations

Abstract

We recorded IR spectra for neutral cobalt clusters via two-color IR-UV ionization, using the Free Electron Laser for intracavity experiments (FELICE). Well-resolved IR spectra are presented for (n = 4–10, 13) and analyzed with the help of Density Functional Theory calculations using two different correlation exchange functionals: the revisited Tao–Perdew–Staroverov–Scuseria (revTPSS) and the frequently used Perdew–Burke–Ernzerhof (PBE) approaches. Although we have not performed an extensive structure search, we tentatively assign the spectra for all cluster sizes except for n = 7, and n = 10. We find that neither of the two functionals chosen clearly outperforms the other in predicting IR spectra, and that relatively low scaling factors of 0.82 (PBE) and 0.8 (revTPSS) are required. In contrast to the magnetic moments, the calculated electric dipole moments fluctuate strongly as a function of cluster size and could therefore be used as an indirect probe to the cluster structure.