Lanthanide Ionization Energies and the Sub-Shell Break. Part 1. The Second Ionization Energies

Johnson, David A. and Nelson, Peter G. (2017). Lanthanide Ionization Energies and the Sub-Shell Break. Part 1. The Second Ionization Energies. Journal of Physical and Chemical Reference Data, 46(1), article no. 013108.

DOI: https://doi.org/10.1063/1.4977958

Abstract

By interpolating a 4f^q6s to 4f^q7s transition within the sequence f¹ to f¹⁴ rather than between f⁰ and f¹⁴, revised second ionization energies of the lanthanides have been obtained. In the early part of the series, between cerium and samarium, the revisions are significantly higher than currently accepted values. The revised values have been used to calculate the energy variation for the conversion of Ln(g, 4f^q6s²) to Ln²⁺(g, 4f^q) across the series Ba to Yb. The variation is smooth between lanthanum and ytterbium but the barium point at q=0 is displaced downwards by more than 0.3 eV, thereby representing a significant sub-shell break. A case is also made for a substantial change to the second ionization energy of lutetium, the revised value being 14.13 ± 0.10 eV.

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