Counter Cations Affect Transport in Aqueous Hydroxide Solutions with Ion Specificity

Chad I. Drexler, Tierney C. Miller, Bradley A. Rogers, Yuguang C. Li, Clyde A. Daly, Tinglu Yang, Steven A. Corcelli, Paul S. Cremer

Research output: Contribution to journalArticlepeer-review

18 Scopus citations


The anomalously high mobility of hydroxide and hydronium ions in aqueous solutions is related to proton transfer and structural diffusion. The role of counterions in these solutions, however, is often considered to be negligible. Herein, we explore the impact of alkali metal counter cations on hydroxide solvation and mobility. Impedance measurements demonstrate that hydroxide mobility is attenuated by lithium relative to sodium and potassium. These results are explained by ab initio molecular dynamics simulations and experimental vibrational hydration shell spectroscopy, which reveal substantially stronger ion pairing between OH- and Li+ than with other cations. Hydration shell spectra and theoretical vibrational frequency calculations together imply that lithium and sodium cations have different effects on the delocalization of water protons donating a hydrogen bond to hydroxide. Specifically, lithium leads to enhanced proton delocalization compared with sodium. However, proton delocalization and the overall diffusion process are not necessarily correlated.

Original languageEnglish (US)
Pages (from-to)6930-6936
Number of pages7
JournalJournal of the American Chemical Society
Issue number17
StatePublished - May 1 2019

All Science Journal Classification (ASJC) codes

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


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