Comprehensive relativistic ab initio and density functional theory studies on PtH, PtF, PtCl, and Pt(NH3)2Cl2

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–Schrödinger 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(NH3)2Cl2 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 C2v isomers of cis‐Pt(NH3)2Cl2 are marginally separated in energy, which could be ascribed to Cl—H interactions. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 564–575, 2002; DOI 10.1002/jcc.10030

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