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:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- 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. https://doi.org/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. https://doi.org/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 = {Fri Jan 02 00:00:00 EST 2015},
month = {Fri Jan 02 00:00:00 EST 2015}
}
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