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Title: Molecular Level Understanding of the Factors Affecting the Stability of Dimethoxy Benzene Catholyte Candidates from First-Principles Investigations

Abstract

First-principles simulations are performed to gain molecular level insights into the factors affecting the stability of seven 1,4-dimethoxybenzene (DMB) derivatives. These molecules are potential catholyte candidates for nonaqueous redox flow battery systems. Computations are performed to predict oxidation potentials in various dielectric mediums, intrinsic-reorganization energies, and structural changes of these representative catholyte molecules during the redox process. In order to understand the stability of the DMB-based radical cations, the thermodynamic feasibility of the following reactions is computed using density functional theory: (a) deprotonation, (b) dimerization, (c) hydrolysis, and (d) demethylation. The computations indicate that radical cations of the 2,3-dimethyl and 2,5-dimethyl derivatives are the most stable among the DMB derivatives considered in this study. In the presence of solvents with high-proton solvating ability (water, DMSO, acetonitrile), degradation of cation radical occurring via deprotonation is the most likely mechanism. In the presence of solvents such as propylene carbonate (PC), demethylation was found to be the most likely reaction that causes degradation of radical cations. From the computed enthalpy of activation (Delta H-double dagger) for a demethylation reaction in PC, the 2,5-dimethyl DMB cation radical would exhibit better kinetic stability in comparison to the other candidates. Finally, this investigation suggests that computationalmore » studies of structural properties such as redox potentials, reorganization energies, and the computed reaction energetics (deprotonation and demethylation) of charged species can be used to predict the relative stability of a large set of molecules required for the discovery of novel redox active materials for flow battery applications« less

Authors:
 [1];  [2];  [2];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Joint Center for Energy Storage Research (JCESR); Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1259933
Alternate Identifier(s):
OSTI ID: 1352881
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 27; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Assary, Rajeev S., Zhang, Lu, Huang, Jinhua, and Curtiss, Larry A. Molecular Level Understanding of the Factors Affecting the Stability of Dimethoxy Benzene Catholyte Candidates from First-Principles Investigations. United States: N. p., 2016. Web. doi:10.1021/acs.jpcc.6b04263.
Assary, Rajeev S., Zhang, Lu, Huang, Jinhua, & Curtiss, Larry A. Molecular Level Understanding of the Factors Affecting the Stability of Dimethoxy Benzene Catholyte Candidates from First-Principles Investigations. United States. doi:10.1021/acs.jpcc.6b04263.
Assary, Rajeev S., Zhang, Lu, Huang, Jinhua, and Curtiss, Larry A. Tue . "Molecular Level Understanding of the Factors Affecting the Stability of Dimethoxy Benzene Catholyte Candidates from First-Principles Investigations". United States. doi:10.1021/acs.jpcc.6b04263.
@article{osti_1259933,
title = {Molecular Level Understanding of the Factors Affecting the Stability of Dimethoxy Benzene Catholyte Candidates from First-Principles Investigations},
author = {Assary, Rajeev S. and Zhang, Lu and Huang, Jinhua and Curtiss, Larry A.},
abstractNote = {First-principles simulations are performed to gain molecular level insights into the factors affecting the stability of seven 1,4-dimethoxybenzene (DMB) derivatives. These molecules are potential catholyte candidates for nonaqueous redox flow battery systems. Computations are performed to predict oxidation potentials in various dielectric mediums, intrinsic-reorganization energies, and structural changes of these representative catholyte molecules during the redox process. In order to understand the stability of the DMB-based radical cations, the thermodynamic feasibility of the following reactions is computed using density functional theory: (a) deprotonation, (b) dimerization, (c) hydrolysis, and (d) demethylation. The computations indicate that radical cations of the 2,3-dimethyl and 2,5-dimethyl derivatives are the most stable among the DMB derivatives considered in this study. In the presence of solvents with high-proton solvating ability (water, DMSO, acetonitrile), degradation of cation radical occurring via deprotonation is the most likely mechanism. In the presence of solvents such as propylene carbonate (PC), demethylation was found to be the most likely reaction that causes degradation of radical cations. From the computed enthalpy of activation (Delta H-double dagger) for a demethylation reaction in PC, the 2,5-dimethyl DMB cation radical would exhibit better kinetic stability in comparison to the other candidates. Finally, this investigation suggests that computational studies of structural properties such as redox potentials, reorganization energies, and the computed reaction energetics (deprotonation and demethylation) of charged species can be used to predict the relative stability of a large set of molecules required for the discovery of novel redox active materials for flow battery applications},
doi = {10.1021/acs.jpcc.6b04263},
journal = {Journal of Physical Chemistry. C},
number = 27,
volume = 120,
place = {United States},
year = {2016},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acs.jpcc.6b04263

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