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An Ab Initio Investigation of the Hydration of Thallium(III) and Mercury(II)

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Abstract

The energies, structures, and vibrational frequencies of M(H2O)n, M = Tl3+, Hg2+, n = 0–9, 18 have been calculated at the Hartree–Fock and second order Møller–Plesset levels of theory using the CEP, LANL2, and SDD effective core potentials in combination with their associated basis sets, or with the 6-31G* and 6-31+G* basis sets. The metal–oxygen distances and totally symmetric stretching frequency of the aqua ions were compared with each other and with solution measurements. The results are consistent with thallium(III) and mercury(II) being hexacoordinate in aqueous solution. The use of symmetry is shown to be advantageous.

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Acknowledgements

The authors thank the Department of Astronomy and Physics, Saint Mary’s University (AP-SMU), for providing access to computing facilities, in particular, to cygnus, a 10-processor Sun server, purchased with assistance from the Canada Foundation for Innovation, Sun Microsystems, the Atlantic Canada Opportunities Agency, and SMU. CCP also thanks ACEnet and Compute Canada for providing access to computers and Gaussian 03/16. CCP acknowledges the former financial support of NSERC. CMG acknowledges the support of the Department of Economic Development (Government of Nova Scotia), the Office of the Dean of Science, SMU, and the Cooperative Education program (SMU—Work Term 1, Summer 2001 and Work Term 2, Fall 2001).

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  1. Department of Chemistry, Saint Mary’s University, Halifax, NS, B3H 3C3, Canada

    Cory C. Pye & C. Mahesh Gunasekara

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  1. Cory C. Pye
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Correspondence to Cory C. Pye.

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Pye, C.C., Gunasekara, C.M. An Ab Initio Investigation of the Hydration of Thallium(III) and Mercury(II). J Solution Chem 49, 1419–1429 (2020). https://doi.org/10.1007/s10953-020-00956-6

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  • DOI: https://doi.org/10.1007/s10953-020-00956-6

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