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Nature of Monomeric Molybdenum(VI) cations in acid solutions using theoretical calculations and raman spectroscopy

Zhang, N., Königsberger, E., Duan, S., Lin, K., Yi, H., Zeng, D., Zhao, Z. and Hefter, G. (2019) Nature of Monomeric Molybdenum(VI) cations in acid solutions using theoretical calculations and raman spectroscopy. The Journal of Physical Chemistry B, 123 (15). pp. 3304-3311.

Link to Published Version: https://doi.org/10.1021/acs.jpcb.9b00926
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Abstract

The composition and structures of the two protonated species formed from uncharged molybdic acid, MoO2(OH)2(OH2)20, in strongly acidic solutions have been investigated using a combination of density functional theory calculations, first-principles molecular dynamics simulations, and Raman spectroscopy. The calculations show that both protonated species maintain the original octahedral structure of molybdic acid. Computed pKa values indicated that the ═O moieties are the proton acceptor sites and, therefore, that MoO(OH)3(OH2)2+ and Mo(OH)4(OH2)22+ are the probable protonated forms of Mo(VI) in strong acid solutions, rather than the previously accepted MoO2(OH)2–x(OH2)2+xx+ (x = 1, 2) species. This finding is shown to be broadly consistent with the observed Raman spectra. Structural details of MoO(OH)3(OH2)2+ and Mo(OH)4(OH2)22+ are reported.

Item Type: Journal Article
Murdoch Affiliation: Chemistry and Physics
Publisher: American Chemical Society
Copyright: © 2019 American Chemical Society
URI: http://researchrepository.murdoch.edu.au/id/eprint/45415
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