@article{35886,
  author = {J. Wayne Mullinax and Charles W Bauschlicher and Kristian B Knudsen and Pedro L Arrechea and Rocco P Viggiano and Donald A Dornbusch and Justin B Haskins and Baochau Nguyen and Bryan D McCloskey and John W Lawson},
  title = {Amide and Urea Based Solvents for Li{\textendash}O2 Batteries. Part II: Evaluation of Decomposition Pathways Using Density Functional Theory},
  abstract = {<p><span>Potential decomposition mechanisms are investigated using density functional theory (DFT) for a set of amide and urea solvents. Reaction energies and barriers are reported for proton and hydrogen abstraction, and preferred abstraction sites are identified. The N{\textendash}H bond of secondary amides and the α-hydrogen atoms are more susceptible to proton abstraction than other sites in the solvent molecules. Additionally, hydrogen abstraction is more favorable at the\&nbsp;</span><em>N</em><span>-alkyl substituents as well as α-hydrogen atoms that result in the formation of secondary and tertiary radicals. All proton abstraction energies are sensitive to the presence of a coordinating Li</span><sup><span>+</span></sup><span>, but the hydrogen abstraction energies do not depend on the presence of a Li</span><sup><span>+</span></sup><span>. The stabilization due to the presence of Li</span><sup><span>+</span></sup><span>\&nbsp;is most pronounced for sites near the carbonyl group where the Li</span><sup><span>+</span></sup><span>\&nbsp;interacts with the lone pair of electrons formed by proton abstraction and the carbonyl O atom. The initial steps of a Baeyer{\textendash}Villiger oxidation type mechanism are also examined. Barriers for these initial steps are significantly lower if HO</span><sub><span>2</span></sub><span>{\textendash}</span><span>\&nbsp;is the oxidant compared to LiO</span><sub><span>2</span></sub><span>{\textendash}</span><span>. A comparison to our previously reported experimental results indicates that no single reaction could be identified as the rate-limiting step that would predict the performance of this set of solvents in Li{\textendash}O</span><sub><span>2</span></sub><span>\&nbsp;batteries.</span></p>},
  year = {2023},
  booktitle = {The Journal of Physical Chemistry C},
  journal = {The Journal of Physical Chemistry C},
  series = {The Journal of Physical Chemistry C},
  volume = {127},
  pages = {7043 - 7053},
  month = {04/2023},
  issn = {1932-7447},
  url = {https://pubs.acs.org/doi/10.1021/acs.jpcc.2c08942},
  doi = {10.1021/acs.jpcc.2c08942},
  language = {eng},
}