Identificador: TDX:4074
Autores: Petrus Pérez, Enric
Resumen:
In this thesis we have developed POMSimulator, a novel computational
method that predicts the aqueous speciation of molecular oxoclusters
as well as the formation mechanism. In our first work we
tested this methodology with a model system: the octamolybdate,
[Mo8O26]4−.1 We reported the speciation diagrams of molybdates
with high accuracy, and we proposed a reaction mechanism considering
the acid-base balance. Next, we extended this methodology
to all the isopolyoxomolybdates and -tungstates.2 We described the
formation of larger clusters such as: [H32Mo36O128]8−, [W12O42]12−,
[W12O40]8−, and [W10O32]4−. Besides, we introduced phase diagrams
in our methodology to obtain a better overview of the speciation
at different concentrations. Recently, we have applied POMSimulator
to polyoxovanadates, -niobates, and tantalates.3 We showed
that accurate formation constants could be computed for the three
metal-oxo systems. We proposed a vanadate intermediate, [V5O14]3−,
which could be involved in the interconversion of the decavanadate,
[V10O28]6−, and the metavanadates, [VnO3n]n− (n=4,5,6). Furthermore,
we reported the speciation diagram of niobates including paramount
clusters such as [H9Nb24O72]15− and [Nb7O22]9−. in conxiii
trast, we found no evidence of the formation of the tantalum analogues.
Nevertheless, we observed the formation of the decatantalate,
[Ta10O28]6−, even though it has not been synthesized yet due to its
poor solubility in water. Overall, we believe that our method can
find a very promising synergy with experimental chemistry.
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Repositori URV