Importance of Spin–Orbit Coupling for the Assignment of the Photodetachment Spectra of AuX2− (X=Cl, Br, and I)

✍ Scribed by Sabyashachi Mishra; Valerie Vallet; Wolfgang Domcke

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 101 KB
• Volume: 7
• Category: Article
• ISSN: 1439-4235
• DOI: 10.1002/cphc.200500554

✦ Synopsis

Abstract

Recently, photodetachment spectra of AuX~2~^−^, X=Cl, Br, and I, have been reported [D. Schröder et al., Angew. Chem. Int. Ed. 2003, 42, 311] followed by a scalar‐relativistic theoretical study of the assignment of these spectra [B. Dai, J. Yang, Chem. Phys. Lett. 2003, 379, 512]. Herein, the photodetachment spectra of the title molecules are reassigned, taking spin–orbit coupling into account and employing relativistic‐effective core potentials for gold and the halogen atoms. The composition of the AuX~2~ electronic states are further analyzed in terms of scalar‐relativistic electronic states. The relevance of spin–orbit coupling in the spectroscopy of heavy elements is emphasized by comparing the results of this work with experiment and with other scalar‐relativistic theoretical studies.