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

N. Zhang; E. Königsberger; S. Duan; K. Lin; H. Yi; D. Zeng; Z. Zhao; G. Hefter

doi:10.1021/acs.jpcb.9b00926

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

Journal article

Peer reviewed

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

N. Zhang, E. Königsberger, S. Duan, K. Lin, H. Yi, D. Zeng, Z. Zhao and G. Hefter

The Journal of Physical Chemistry B, Vol.123(15), pp.3304-3311

2019

DOI: 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.

Details

Title: Nature of Monomeric Molybdenum(VI) cations in acid solutions using theoretical calculations and raman spectroscopy
Authors/Creators: N. Zhang (Author/Creator)
E. Königsberger (Author/Creator) - Murdoch University
S. Duan (Author/Creator) - Xidian University
K. Lin (Author/Creator) - Xidian University
H. Yi (Author/Creator) - Hunan University
D. Zeng (Author/Creator) - Hunan University
Z. Zhao (Author/Creator)
G. Hefter (Author/Creator) - Murdoch University
Publication Details: The Journal of Physical Chemistry B, Vol.123(15), pp.3304-3311
Publisher: American Chemical Society
Identifiers: 991005540163507891
Murdoch Affiliation: Chemistry and Physics
Language: English
Resource Type: Journal article

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Collaboration types: Domestic collaboration; International collaboration
Citation topics: 2 Chemistry; 2.22 Inorganic & Nuclear Chemistry; 2.22.1074 Polyoxometalates
Web Of Science research areas: Chemistry, Physical
ESI research areas: Chemistry