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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. As a result, 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.

Authors:
 [1];  [1];  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1183827
Report Number(s):
BNL-107848-2015-JA
Journal ID: ISSN 0002-7863; R&D Project: CO004; KC0304030
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 137; Journal Issue: 3; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Mani, Tomoyasu, Grills, David C., and Miller, John R. Vibrational stark effects to identify ion pairing and determine reduction potentials in electrolyte-free environments. United States: N. p., 2015. Web. doi:10.1021/ja512302c.
Mani, Tomoyasu, Grills, David C., & Miller, John R. Vibrational stark effects to identify ion pairing and determine reduction potentials in electrolyte-free environments. United States. doi:10.1021/ja512302c.
Mani, Tomoyasu, Grills, David C., and Miller, John R. Fri . "Vibrational stark effects to identify ion pairing and determine reduction potentials in electrolyte-free environments". United States. doi:10.1021/ja512302c. https://www.osti.gov/servlets/purl/1183827.
@article{osti_1183827,
title = {Vibrational stark effects to identify ion pairing and determine reduction potentials in electrolyte-free environments},
author = {Mani, Tomoyasu and Grills, David C. and Miller, John R.},
abstractNote = {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. As a result, 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.},
doi = {10.1021/ja512302c},
journal = {Journal of the American Chemical Society},
number = 3,
volume = 137,
place = {United States},
year = {2015},
month = {1}
}

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