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

16 Citations (Scopus)

Abstract

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
Volume137
Issue number3
DOIs
Publication statusPublished - Jan 28 2015

Fingerprint

Stark effect
Electrolytes
Ions
Pulse Radiolysis
Free Association
Radiolysis
Vibrational spectra
Free energy
Anions
Permittivity
Negative ions
Association reactions
Infrared radiation
Molecules
Geometry

ASJC Scopus subject areas

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

Cite this

Vibrational stark effects to identify ion pairing and determine reduction potentials in electrolyte-free environments. / Mani, Tomoyasu; Grills, David; Miller, John R.

In: Journal of the American Chemical Society, Vol. 137, No. 3, 28.01.2015, p. 1136-1140.

Research output: Contribution to journalArticle

@article{9eed9025ed21431eaeaacef74b16131b,
title = "Vibrational stark effects to identify ion pairing and determine reduction potentials in electrolyte-free environments",
abstract = "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).",
author = "Tomoyasu Mani and David Grills and Miller, {John R.}",
year = "2015",
month = "1",
day = "28",
doi = "10.1021/ja512302c",
language = "English",
volume = "137",
pages = "1136--1140",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "3",

}

TY - JOUR

T1 - Vibrational stark effects to identify ion pairing and determine reduction potentials in electrolyte-free environments

AU - Mani, Tomoyasu

AU - Grills, David

AU - Miller, John R.

PY - 2015/1/28

Y1 - 2015/1/28

N2 - 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).

AB - 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).

UR - http://www.scopus.com/inward/record.url?scp=84921920997&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84921920997&partnerID=8YFLogxK

U2 - 10.1021/ja512302c

DO - 10.1021/ja512302c

M3 - Article

VL - 137

SP - 1136

EP - 1140

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 3

ER -