Predicting the stability of aprotic solvents in Li-air batteries: PK a calculations of aliphatic C-H acids in dimethyl sulfoxide

Vyacheslav S. Bryantsev

doi:10.1016/j.cplett.2012.12.066

Predicting the stability of aprotic solvents in Li-air batteries: PK _a calculations of aliphatic C-H acids in dimethyl sulfoxide

Vyacheslav S. Bryantsev

Research output: Contribution to journal › Article › peer-review

47 Scopus citations

Abstract

Superoxide is a strong base that can induce base-catalyzed autoxidation of weakly acidic solvents. We report on the performance of several computational protocols for predicting pK_a values for a wide range of aliphatic C-H acids in DMSO. Calculations at the MP2/CBS level with CCSD(T)/aug-cc-pVDZ corrections and solvent effects calculated using the SVPE model provide the best overall performance (rms deviation is 0.65 pK_a). The B3LYP, M06, and M06-2X functionals can also achieve high accuracy (<1 pK_a) by employing empirical corrections to fit the experimental data. Computational results provide a convenient means of screening for suitable solvents in Li-air batteries.

Original language	English
Pages (from-to)	42-47
Number of pages	6
Journal	Chemical Physics Letters
Volume	558
DOIs	https://doi.org/10.1016/j.cplett.2012.12.066
State	Published - Feb 12 2013
Externally published	Yes

Funding

This work is supported by Liox Power, Inc. , Pasadena, CA.

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10.1016/j.cplett.2012.12.066

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title = "Predicting the stability of aprotic solvents in Li-air batteries: PK a calculations of aliphatic C-H acids in dimethyl sulfoxide",

abstract = "Superoxide is a strong base that can induce base-catalyzed autoxidation of weakly acidic solvents. We report on the performance of several computational protocols for predicting pKa values for a wide range of aliphatic C-H acids in DMSO. Calculations at the MP2/CBS level with CCSD(T)/aug-cc-pVDZ corrections and solvent effects calculated using the SVPE model provide the best overall performance (rms deviation is 0.65 pKa). The B3LYP, M06, and M06-2X functionals can also achieve high accuracy (<1 pKa) by employing empirical corrections to fit the experimental data. Computational results provide a convenient means of screening for suitable solvents in Li-air batteries.",

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T2 - PK a calculations of aliphatic C-H acids in dimethyl sulfoxide

AU - Bryantsev, Vyacheslav S.

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N2 - Superoxide is a strong base that can induce base-catalyzed autoxidation of weakly acidic solvents. We report on the performance of several computational protocols for predicting pKa values for a wide range of aliphatic C-H acids in DMSO. Calculations at the MP2/CBS level with CCSD(T)/aug-cc-pVDZ corrections and solvent effects calculated using the SVPE model provide the best overall performance (rms deviation is 0.65 pKa). The B3LYP, M06, and M06-2X functionals can also achieve high accuracy (<1 pKa) by employing empirical corrections to fit the experimental data. Computational results provide a convenient means of screening for suitable solvents in Li-air batteries.

AB - Superoxide is a strong base that can induce base-catalyzed autoxidation of weakly acidic solvents. We report on the performance of several computational protocols for predicting pKa values for a wide range of aliphatic C-H acids in DMSO. Calculations at the MP2/CBS level with CCSD(T)/aug-cc-pVDZ corrections and solvent effects calculated using the SVPE model provide the best overall performance (rms deviation is 0.65 pKa). The B3LYP, M06, and M06-2X functionals can also achieve high accuracy (<1 pKa) by employing empirical corrections to fit the experimental data. Computational results provide a convenient means of screening for suitable solvents in Li-air batteries.

UR - https://www.scopus.com/pages/publications/84873207328

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M3 - Article

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EP - 47

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -

Predicting the stability of aprotic solvents in Li-air batteries: PK _a calculations of aliphatic C-H acids in dimethyl sulfoxide

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