Comparative study of electronic-structure methods for platinum-containing molecules: bond lengths and bond dissociation energies⋆,,⋆⋆
Institute of Ion Physics and Applied Physics, University of Innsbruck, Technikerstraße 25, 6020 Innsbruck, Austria
Received in final form: 3 April 2019
Published online: 2 July 2019
We compare various electronic structure methods including a broad range of density functionals with experimental data on bond lengths and bond dissociation energies available for di- and triatomic platinum-containing molecules. In total we employ 54 GGA, 17 meta-GGA, 36 hybrid, 103 mixed GGA/meta GGA, 17 hybrid, 7 meta hybrid, 10 range-separated hybrid and 5 double hybrid density functionals. Furthermore, the performance of ab initio methods including Hartree-Fock, Møller-Plesset perturbation theory up to fourth order as well as coupled cluster theory up to perturbatively approximated triple excitations, i.e. CCSD(T), is also investigated. In the case of bond lengths, the smallest mean average deviation from experimental values yielding 0.3 pm is found for the hybrid density functional TPSSh. Interestingly, neither recent double hybrid functionals nor ab initio methods result in similar, commensurable accuracies. For the investigated bond dissociation energies, the GGA functional TPSSVWN5 is the closest to experiment with deviations of 6.97 kcal/mol. Finally, we address various possible sources of errors that may explain the large mean average deviation from experiment in the case of CCSD(T) (8.87 kcal/mol), including the effect of basis set size, the influence of the multireference character of the molecular wave function, the quality of the HF determinant as reference wave function and the influence of core electron correlation.
Contribution to the Topical Issue “Dynamics of Systems on the Nanoscale (2018)”, edited by Ilko Bald, Ilia A. Solov’yov, Nigel J. Mason and Andrey V. Solov’yov.
Supplementary material in the form of one pdf file available from the Journal web page at https://doi.org/10.1140/epjd/e2019-90691-1
© The Author(s) 2019. This article is published with open access at Springerlink.com
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Open access funding provided by Austrian Science Fund (FWF).