Comprehensive relativistic ab initio and density functional theory studies on PtH, PtF, PtCl, and Pt(NH3)2Cl2
β Scribed by Wenjian Liu; Robert Franke
- Publisher
- John Wiley and Sons
- Year
- 2002
- Tongue
- English
- Weight
- 134 KB
- Volume
- 23
- Category
- Article
- ISSN
- 0192-8651
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β¦ Synopsis
Platinum monohydride is taken as an example to compare the performance of various relativistic and correlation approaches, such as all-electron DPT (direct perturbation theory), ECP (effective core potential); RSPT2, RSPT3 (second- and third-order multireference Rayleigh-SchrΓΆdinger perturbation theory), CCSD(T) (coupled-cluster with singles, doubles, and perturbative triples), as well as the four-component relativistic density functional theory. It is shown that first-order DPT performs significantly better than the (first-order) Breit-Pauli Hamiltonian. The performance of different approaches for the excitation energies of the platinum diatomics is discussed critically. The molecular spectroscopic constants for PtF and PtCl are predicted for the first time. The geometric data for several isomers of cis- and trans-Pt(NH(3))(2)Cl(2) are reported. The corresponding energetic data are calculated at relativistic all-electron and ECP-CCSD(T) as well as four-component relativistic density functional levels of theory. Contrary to previous results, it is found that the two C(2v) isomers of cis-Pt(NH(3))(2)Cl(2) are marginally separated in energy, which could be ascribed to Cl-H interactions.
π SIMILAR VOLUMES
## Abstract We present a direct __ab initio__ and hybrid density functional theory dynamics study of the thermal rate constants of the unimolecular decomposition reaction of C~2~H~5~O β CH~2~O + CH~3~ at a highβpressure limit. MPW1K/6β31+G(d,p), MP2/6β31+G(d,p), and MP2(full)/6β31G(d) methods were