Abstract.
Relativistic energy-consistent small-core lanthanide pseudopotentials of the Stuttgart–Bonn variety and extended valence basis sets have been used for the investigation of the dimers La2 and Lu2. It was found that the ground states for La2 and Lu2 are most likely 1∑ g + (σ g 2π u 4) and 3∑ g − (4f 144f 14σ g 2σ u 2πu 2), respectively. The molecular constants including error bars were derived from multireference configuration interaction as well as coupled-cluster calculations, taking into account corrections for atomic spin–orbit splitting as well as possible basis set superposition errors. The theoretical values for La2 (R e=2.70±0.03 Å, D e=2.31±0.13 eV, ωe=186±13 cm−1) show good agreement with the experimental binding energy (D e=2.52±0.22 eV), but the experimental vibrational constant in an Ar matrix (ωe=236±0.8 cm−1) is significantly higher. For Lu2 the theoretical values (R e=3.07±0.03 Å, D e=1.40±0.12 eV, ωe=123±1 cm−1) are in overall excellent agreement with experimental data (D e=1.43±0.34 eV, ωe=122± 1 cm−1). The electronic structures of La2 and Lu2 are compared to those other lanthanide dimers and trends in the series are discussed.
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Received: 25 March 2002 / Accepted: 2 June 2002 / Published online: 21 August 2002
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Cao, X., Dolg, M. Pseudopotential study of lanthanum and lutetium dimers. Theor Chem Acc 108, 143–149 (2002). https://doi.org/10.1007/s00214-002-0372-8
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DOI: https://doi.org/10.1007/s00214-002-0372-8