Correction: Insights into the enhanced Ce[triple bond, length as m-dash]N triple bond in the HCe[triple bond, length as m-dash]N molecule.

Correction for 'Insights into the enhanced Ce[triple bond, length as m-dash]N triple bond in the HCe[triple bond, length as m-dash]N molecule' by Zhen Pu et al., Phys. Chem. Chem. Phys., 2017, 19, 8216-8222.

Insights into the enhanced Ce[triple bond, length as m-dash]N triple bond in the HCe[triple bond, length as m-dash]N molecule.

Herein, an experimental study of the vibrational spectra of HCeN was carried out in solid argon, followed by theoretical investigations of molecular structures and the nature of Ce[triple bond, length as m-dash]N bond. The absorption band at 937.7 cm-1 with the 1.0311 14N/15N isotopic shift ratio is characteristic of Ce[triple bond, length as m-dash]N stretching band for HCeN, showing a 94 cm-1 higher shift relative to that of the diatomic CeN molecule. This large frequency shift indicates a much stronger Ce[triple bond, length as m-dash]N bond in HCeN, which is confirmed by DFT calculations. Qualitative orbital interaction and orbital composition analyses suggest that the addition of the H ligand to the Ce center will activate the 4f valence shell and strengthen the covalent bond between Ce and N, which may contribute to enhance the Ce[triple bond, length as m-dash]N triple bond in the HCeN molecule.

A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO(-).

The observation of the gaseous UFO(-) anion is reported, which is investigated using photoelectron spectroscopy and relativisitic ab initio calculations. Two strong photoelectron bands are observed at low binding energies due to electron detachment from the U-7sσ orbital. Numerous weak detachment bands are also observed due to the strongly correlated U-5f electrons. The electron affinity of UFO is measured to be 1.27(3) eV. High-level relativistic quantum chemical calculations have been carried out on the ground state and many low-lying excited states of UFO to help interpret the photoelectron spectra and understand the electronic structure of UFO. The ground state of UFO(-) is linear with an O-U-F structure and a (3)H4 spectral term derived from a U 7sσ(2)5fφ(1)5fδ(1) electron configuration, whereas the ground state of neutral UFO has a (4)H(7/2) spectral term with a U 7sσ(1)5fφ(1)5fδ(1) electron configuration. Strong electron correlation effects are found in both the anionic and neutral electronic configurations. In the UFO neutral, a high density of electronic states with strong configuration mixing is observed in most of the scalar relativistic and spin-orbit coupled states. The strong electron correlation, state mixing, and spin-orbit coupling of the electronic states make the excited states of UFO very challenging for accurate quantum chemical calculations.