Effect of Basicity on the Hydrolysis of the Bi(III) Aqua Ion in Solution: An Ab Initio Molecular Dynamics Study

Abstract

Hydrolysis of the Bi(III) aqua ion under a range of solution conditions has been studied by means of ab initio molecular dynamics simulations. While the Bi(III) aqua ion is stable in pure water, there is an increasing degree of hydrolysis with the number of hydroxide anions in the medium. This is accompanied by a monotonic decrease of the total coordination number to an asymptotic value of ∼6, reached under extreme basicity conditions. Comparison of the simulated Bi(III) hydrolyzed species with the experimental species distribution at different degrees of basicity suggests that, at the PBE/DFT level of theory here employed, liquid water shows an overly acidic character. Predictions of theoretical EXAFS and XANES spectra were generated from the AIMD trajectories for different Bi hydrolyzed species, [Bi(HO)(HO)], m = 0-3 and n = 7-2. Comparison with available experimental spectra is presented. Spectral features joined to the degree of hydrolysis and hydration are analyzed.

Mesoporous PdBi nanocages for enhanced electrocatalytic performances by all-direction accessibility and steric site activation

“…S6 †). 25,26 Moreover, the acid concentration imparts pore regulations to the mesoporous shells. A relatively low growth speed at a higher acid concentration benets the formation of ordered mesoporous shells, thus resulting in well-organized nanocages (Fig.…”

Advanced X-ray Shielding Materials Enabled by the Coordination of Well-Dispersed High Atomic Number Elements in Natural Leather

“…As the interactions between the functional groups of LM and bismuth iodide were observed by XPS, we preformed theoretical calculations for further investigations. According to the simulations, bismuth­(III) exists mainly as BiI 2+ and Bi­(OH) 2 + species (Figure S9) and often form hexadentate BiI­(H 2 O) 5 2+ and Bi­(OH) 2 (H 2 O) 4 + hydrated ions (Figure S10) in the experimental pH range . The same simulations were carried out for iodine, and the results showed that besides the aforementioned BiI 2+ , the only existed form of iodine was I – .…”

“…According to the simulations, bismuth(III) exists mainly as BiI 2+ and Bi(OH) 2 + species (Figure S9) and often form hexadentate BiI(H 2 O) 5 2+ and Bi(OH) 2 (H 2 O) 4 + hydrated ions (Figure S10) in the experimental pH range. 25 The same simulations were carried out for iodine, and the results showed that besides the aforementioned BiI 2+ , the only existed form of iodine was I − . Since collagen triple helices, the fundamental molecular building blocks of LM, were comprised of 18 amino acids, 26 we classified these amino acids into three categories negatively charged amino acids, positively charged amino acids along with uncharged amino acids, and picked out one or two typical amino acids in each category to perform the theoretical calculations.…”

Electrodialytic Enrichment and Matrix Conversion for the Determination of Trace Metals in Ultra-Pure Water

“…Under neutral pH, Ga(OH) 4 – is formed 16 and transferred into the anode side isolator solution or trapped by AEM. On the other hand, Bi(OH) 4 – is formed at pH higher than 10.5, 15 and the removal of Bi 3+ shifted the equilibrium of Bi species and quantitative transfer was achieved at relatively low concentrations. The details of the calibration curves, equations, and correlation coefficients are also summarized in Table S3 .…”