College of Science , Central South University of Forestry and Technology , Changsha 410004 , Hunan , P.R. China.
College of Chemistry and Chemical Engineering , Hunan University , Changsha 410082 , Hunan , P.R. China.
J Phys Chem B. 2019 Apr 18;123(15):3304-3311. doi: 10.1021/acs.jpcb.9b00926. Epub 2019 Apr 9.
The composition and structures of the two protonated species formed from uncharged molybdic acid, MoO(OH)(OH), 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 p K values indicated that the ═O moieties are the proton acceptor sites and, therefore, that MoO(OH)(OH) and Mo(OH)(OH) are the probable protonated forms of Mo(VI) in strong acid solutions, rather than the previously accepted MoO(OH)(OH) ( x = 1, 2) species. This finding is shown to be broadly consistent with the observed Raman spectra. Structural details of MoO(OH)(OH) and Mo(OH)(OH) are reported.
使用密度泛函理论计算、第一性原理分子动力学模拟和拉曼光谱相结合的方法，研究了在强酸性溶液中未带电钼酸（MoO(OH)(OH)）形成的两种质子化物种的组成和结构。计算表明，两种质子化物种都保持了钼酸的原始八面体结构。计算的 pK 值表明，═O 部分是质子受体位点，因此，MoO(OH)(OH)和 Mo(OH)(OH)是 Mo(VI)在强酸溶液中的可能质子化形式，而不是先前接受的 MoO(OH)(OH)（x=1，2）物种。这一发现与观察到的拉曼光谱广泛一致。报道了 MoO(OH)(OH)和 Mo(OH)(OH)的结构细节。
