A Comparative Ab Initio Study of the Primary Hydration and Proton Dissociation of Various Imide and Sulfonic Acid Ionomers
We compare the role of neighboring group substitutions on proton dissociation of hydrated acidic moieties suitable for proton exchange membranes through electronic structure calculations. Three pairs of ionomers containing similar electron withdrawing groups within the pair were chosen for the study: two fully fluorinated sulfonyl imides (CF3SO2NHSO2CF3 and CF3CF2SO2NHSO2CF3), two partially fluorinated sulfonyl imides (CH3SO2NHSO2CF3 and C6H5SO2NHSO2CF2CF3), and two aromatic sulfonic acid based material s (CH3C6H4SO3H and CH3 OC6 - H3OCH3C6H4SO3H). Fully optimized counterpoise (CP) corrected geometries were obtained for each ionomer fragment with the inclusion of water molecules at the B3LYP/6-311G** level of density functional theory. Spontaneous proton dissociation was observed upon addition of three water molecules in each system, and the transition to a solvent-separated ion pair occurred when four water molecules were introduced. No considerable quantitative or qualitative differences in proton dissociation, hydrogen bond networks formed, or water binding energies were found between systems containing similar electron withdrawing groups. Each of the sulfonyl imide ionomers exhibited qualitatively similar results regarding proton dissociation and separation. The fully fluorinated sulfonyl imides, however, showed a greater propensity to exist in dissociated and ion-pair separated states at low degrees of hydration than the partially fluorinated sulfonyl imides. This effect is due to the additional electron withdrawing groups providing charge stabilization as the dissociated proton migrates away from the imide anion.
- Research Organization:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1047360
- Report Number(s):
- PNNL-SA-86795; KC0302020
- Journal Information:
- Journal of Physical Chemistry A, Journal Name: Journal of Physical Chemistry A Journal Issue: 7 Vol. 116
- Country of Publication:
- United States
- Language:
- English
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