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

46 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.

Funders	Funder number
Liox Power, Inc.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1016/j.cplett.2012.12.066

Cite this

@article{946fc443f77a4172be8fb46b47eaf043,

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.",

author = "Bryantsev, {Vyacheslav S.}",

year = "2013",

month = feb,

day = "12",

doi = "10.1016/j.cplett.2012.12.066",

language = "English",

volume = "558",

pages = "42--47",

journal = "Chemical Physics Letters",

issn = "0009-2614",

publisher = "Elsevier",

}

TY - JOUR

T1 - Predicting the stability of aprotic solvents in Li-air batteries

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

AU - Bryantsev, Vyacheslav S.

PY - 2013/2/12

Y1 - 2013/2/12

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 - http://www.scopus.com/inward/record.url?scp=84873207328&partnerID=8YFLogxK

U2 - 10.1016/j.cplett.2012.12.066

DO - 10.1016/j.cplett.2012.12.066

M3 - Article

AN - SCOPUS:84873207328

SN - 0009-2614

VL - 558

SP - 42

EP - 47

JO - Chemical Physics Letters

JF - Chemical Physics Letters

ER -