bases like KOH NaOH K2CO3 Na2CO3 Cs2CO3 NaHCO3 will have varying pKb values in different solvents with varying temperature. Can anyone let me know if there is any computational method to determine basicity of those bases in a given condition?
Dear Mayukh Majumder, I not really involved in this area of research, but I know that part of Pearson's HSAB theory use the quantum approach to get data from orbitals of electrophiles and nucleophiles. Please check the following documents. My Regards
10.1021/tx2003257
https://www.ch.ic.ac.uk/rzepa/watoc96/abstracts/27/
https://doi.org/10.1039/B606877D
Hi Mayukh Majumder
This is one of the biggest challenges for researchers using DFT caclulations. As you are aware, acidity and basicity are highly dependent on solvent. For example, HCl is not an acid (in the experimental sense) in the gas-phase. When performing calculations in solvent (using models such as SMD), the stabilization of cations is much less of an issue when especially when compared to the errors in solvation of anions (errors can be of the order of ~150 kcal/mol).
In my own research, I have been working on predicting MeOH > MeO- + H+, and I found that solvation of methoxide was always an issue, no matter which method I used. I managed to get a work-around by adding the free energy of solvation of methoxide to its gas-phase free energy (feel free to use this strategy, details of which have been published in the computational section of ChemSci, 2021, 12, 2960). You may also want to look up Pliego's and Ivo Leito's papers; they specialize in compuational prediction of acidities and basicities and/or stabilization of ionic species.
https://scholar.google.com/citations?user=Mf10IccAAAAJ&hl=en
https://scholar.google.com.br/citations?user=yRc91EAAAAAJ&hl=pt-BR
Best,
Shrin
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