Ab initio molecular dynamics investigation of beryllium complexes
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Structures of aqueous [Be(H2O)4]2+, its outer-sphere and inner-sphere complexes with F-, Cl- and SO42-, as well as dinuclear complexes with a [Be(κ-OH)(κ-SO4)]+ core have been studied through Car-Parrinello molecular dynamics (CPMD) simulations with the BLYP functional. According to constrained CPMD/BLYP simulations and pointwise thermodynamic integration, the free energy of deprotonation of [Be(H2O)4]2+ and its binding free energy with F- are 9.6 kcal mol-1 and -6.2 kcal mol-1, respectively, in good accord with available experimental data. The computed activation barriers for replacing a water ligand in [Be(H2O)4]2+ with F- and SO42-, 10.9 kcal mol-1 and 13.6 kcal mol-1, respectively, are also in good qualitative agreement with available experimental data. These ligand substitution reactions are indicated to follow associative interchange mechanisms with backside (SN2-like) attack of the anion relative to the aquo ligand it is displacing. Outperforming static DFT computations of the salient kinetic and thermodynamic quantities involving simple polarizable continuum solvent models, CPMD simulations are validated as a promising tool to study structures and speciation of beryllium complexes in aqueous solution.
Raymond , O , Buehl , M , Lane , J , Henderson , W , Brothers , P & Plieger , P 2020 , ' Ab initio molecular dynamics investigation of beryllium complexes ' , Inorganic Chemistry , vol. Articles ASAP . https://doi.org/10.1021/acs.inorgchem.9b03309
Copyright © 2020 American Chemical Society. This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1021/acs.inorgchem.9b03309
DescriptionAuthors thank EaStCHEM and the School of Chemistry in St Andrews for support. OR thanks the Marsden Fund of the New Zealand Government (contract MAU1204), administered by the Royal Society of New Zealand for financial support of this work.
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