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Electronic structure of the PdCl 4 2− and PtCl 4 2− ions
Author(s) -
Larsson Sven,
Olsson LarsFride,
Rosén Arne
Publication year - 1984
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.560250116
Subject(s) - spectral line , ion , chemistry , ab initio , spectrum (functional analysis) , atomic physics , electronic structure , ab initio quantum chemistry methods , interpretation (philosophy) , physics , computational chemistry , quantum mechanics , molecule , computer science , programming language , organic chemistry
The electronic spectra of PdCl 4 2− and PtCl 4 2− are studied by quantum‐chemical methods with the ultimate object being to understand the differences in reactivity for Pt(II) and Pd(II) complexes. Nonrelativistic ab initio UHF , DV ‐ Xα, and MS Xα methods give very similar assignments of the spectra for PdCl 4 2− . The d – d spectrum for PtCl 4 2− , which is very different from the d – d spectrum of PdCl 4 2− , agrees qualitatively with the spectra obtained using the relativistic extended‐Hückel ( REX ) and Dirac–Slater ( DS ) methods. Although the latter two methods disagree somewhat in the interpretation of the high intensity bands in PtCl 4 2− , it appears reasonable to interpret at least one of the lines as a 5 d → 6 p transition.