Vibrational stark effects to identify ion pairing and determine reduction potentials in electrolyte-free environments

Tomoyasu Mani, David Grills, John R. Miller

Research output: Contribution to journalArticle

17 Citations (Scopus)


A recently developed instrument for time-resolved infrared detection following pulse radiolysis has been used to measure the ν(C≡N) IR band of the radical anion of a CN-substituted fluorene in tetrahydrofuran. Specific vibrational frequencies can exhibit distinct frequency shifts due to ion pairing, which can be explained in the framework of the vibrational Stark effect. Measurements of the ratio of free ions and ion pairs in different electrolyte concentrations allowed us to obtain an association constant and free energy change for ion pairing. This new method has the potential to probe the geometry of ion pairing and allows the reduction potentials of molecules to be determined in the absence of electrolyte in an environment of low dielectric constant. (Graph Presented).

Original languageEnglish
Pages (from-to)1136-1140
Number of pages5
JournalJournal of the American Chemical Society
Issue number3
Publication statusPublished - Jan 28 2015


ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry
  • Medicine(all)

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