| Dependence of pK(a) on solute cavity for diprotic and triprotic acids. | |
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MedLine Citation:
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PMID: 21528149 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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A systematic study of ΔG(aq)/pK(a) for monoprotic, diprotic, and triprotic acids has been carried out based on DFT/aug-cc-pVTZ combined with CPCM and SMD solvation modeling. All DFT/cavity set combinations considered showed similar accuracy for ΔG(aq)(1)/pK(a1) (70% within ±2.5 kcal mol(-1) of experiment) while only the M05-2X/Pauling cavity combination gave reasonable results for ΔG(aq)(2)/pK(a2) when both pK(a) values are separated by more than three units (70% within ±5.0 kcal mol(-1) of experiment). The choice of experimental data is critical to the interpretation of the calculated accuracy especially for several inorganic acids. For the calculation of ΔG(aq)(3)/pK(a3), the larger experimental uncertainty and an unrealistic orbital population of diffuse function for trianions in the gas phase hinders an evaluation of the predictive performance. We find the M05-2X functional with the Pauling cavity set is the best choice for ΔG(aq)(2)/pK(a2) prediction in aqueous media while all DFT/cavity sets considered were competitive for ΔG(aq)(1)/pK(a1). |
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Authors:
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Tae Bum Lee; Michael L McKee |
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Publication Detail:
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Type: JOURNAL ARTICLE Date: 2011-4-28 |
Journal Detail:
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Title: Physical chemistry chemical physics : PCCP Volume: - ISSN: 1463-9084 ISO Abbreviation: - Publication Date: 2011 Apr |
Date Detail:
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Created Date: 2011-4-29 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 100888160 Medline TA: Phys Chem Chem Phys Country: - |
Other Details:
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Languages: ENG Pagination: - Citation Subset: - |
Affiliation:
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Department of Chemistry and Biochemistry, Auburn University, Auburn, Alabama 36849, USA. mckee@chem.auburn.edu. |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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