Vibrational stark effects to identify ion pairing and determine reduction potentials in electrolyte-free environments [electronic resource].
- Published:
- Washington, D.C. : United States. Dept. of Energy. Office of Basic Energy Sciences, 2015.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy - Physical Description:
- pages 1,136-1,140 : digital, PDF file
- Additional Creators:
- Brookhaven National Laboratory
United States. Department of Energy. Office of Basic Energy Sciences
United States. Department of Energy. Office of Scientific and Technical Information - Access Online:
- www.osti.gov
- Summary:
- 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.
- Subject(s):
- Note:
- Published through SciTech Connect.
01/02/2015.
"bnl--107848-2015-ja"
"KC0304030"
Journal of the American Chemical Society 137 3 ISSN 0002-7863 AM
Mani, Tomoyasu; Grills, David; Miller, John. - Funding Information:
- SC00112704
CO004
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