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Updated: May 25, 2026

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
When does the non-variational nature of second-order Møller-Plesset energies manifest itself? All-electron
Shane P McCarthy1, Ajit J Thakkar
1Department of Chemistry, University of New Brunswick, Fredericton, New Brunswick E3B 5A3, Canada.
Abstract:
All-electron correlation energies E(c) are not very well known for open-shell atoms with more than 18 electrons. The complete basis-set (CBS) limits of second-order Møller-Plesset (MP2) perturbation theory energies are obtained for open-shell atoms by computations in large basis sets combined with a knowledge of the MP2/CBS limit for the next larger closed-shell atom with the same valence shell structure. Then higher-order correlation corrections are found by coupled-cluster calculations using basis sets that are not quite as large. The method is validated for the open-shell atoms from Al to Cl for which E(c) is reasonably well established. Then, the method is used to obtain non-relativistic E(c) values, probably accurate to 3%, for the open-shell atoms of the fourth period: K, Sc-Cu, and Ga-Br. These energies are compared with the predictions of 19 density functionals and may be useful for the parameterization of new ones. The results show that MP2 overestimates |E(c)| for atoms heavier than Fe.
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