Relativistic and correlated all-electron calculations on the ground and excited states of AgH and AuH
β Scribed by Witek, Henryk A.; Nakijima, Takahito; Hirao, Kimihiko
- Book ID
- 121707978
- Publisher
- American Institute of Physics
- Year
- 2000
- Tongue
- English
- Weight
- 330 KB
- Volume
- 113
- Category
- Article
- ISSN
- 0021-9606
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β¦ Synopsis
We report relativistic all-electron multireference based perturbation calculations on the low-lying excited states of gold and silver hydrides. For AuH, we consider all molecular states dissociating to the Au(2S)+H(2S) and Au(2D)+H(2S) atomic limits, and for AgH, the states corresponding to the Ag(2S)+H(2S),βAg(2P)+H(2S), and Ag(2D)+H(2S) dissociation channels. Spin-free relativistic effects and the correlation effects are treated on the same footing through the relativistic scheme of eliminating small components (RESC). Spinβorbit effects are included perturbatively. The calculated potential energy curves for AgH are the first reported in the literature. The computed spectroscopic properties agree well with experimental findings; however, the assignment of states does not correspond to our calculations. Therefore, we give a reinterpretation of the experimentally observed Cβ1Ξ ,βaβ3Ξ ,βBβ1Ξ£+,βb(3Ξ1)1,βDβ1Ξ ,βc13Ξ 1, and c0(3Ξ 0) states. A labeling suggested by us is a1,βC0+,βb0β,βc2,βB3Ξ 0+,βd3Ξ 1,βe1,βf1 and g1, respectively. The spinβorbit states corresponding to Ag(2D)+H(2S) have not well defined the Ξ and S quantum numbers, and therefore, they probably correspond to Hundβs coupling case c. For AuH, we present a comparison of the calculated potential energy curves and spectroscopic parameters with the previous configuration interaction study and the experiment.
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