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Thermochemical spin‐orbit corrections for platinum cation (Pt + )
Author(s) -
Irikura Karl K.
Publication year - 2021
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26448
Subject(s) - spin–orbit interaction , thermochemistry , orbit (dynamics) , ground state , atomic physics , excitation , platinum , chemistry , spin (aerodynamics) , physics , thermodynamics , quantum mechanics , biochemistry , engineering , aerospace engineering , catalysis
In quantum thermochemistry, many atoms require spin‐orbit corrections to compensate for the lack of spin‐orbit coupling in most calculations. When terms or configurations are strongly mixed, as they are in Pt + , naïve averaging of experimental data produces erroneous corrections. Here, spin‐orbit calculations provide the composition of observed energy levels in LS (Russell‐Saunders) terms. The compositional data are combined with the experimental energy levels to obtain averaged term energies for Pt + , including the ground‐term spin‐orbit correction. For ground‐state Pt + , a correction of (−4251 ± 136) cm −1 or (−50.8 ± 1.6) kJ mol −1 is recommended. The recommended value for the 2 D‐ 4 F excitation energy, which represents the nominal 5 d ‐6 s promotion energy, is (7112 ± 225) cm −1 . For anionic Pt − , simple J ‐averaging is appropriate, and the ground‐state spin‐orbit correction is (−3896.4 ± 0.2) cm −1 or (−46.611 ± 0.002) kJ mol −1 .