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

Zhang, N., Königsberger, E.ORCID: 0000-0002-4606-0741, 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.

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(s):	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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