Journal article
Dynamics of Excess Electronic Charge in Aliphatic Ionic Liquids Containing the Bis(trifluoromethylsulfonyl)amide Anion
Journal of the American Chemical Society, Vol.135(46), pp.17528-17536
11/20/2013
DOI: 10.1021/ja409338z
PMID: 24156701
Abstract
In a recent article (J. Am. Chem. Soc. 2011, 133, 20186) we investigated the initial spatial distribution of dry excess electrons in a series of room-temperature ionic liquids (RTILs). Perhaps unexpectedly, we found that in some alkylammonium-based systems the excess negative charge resided on anions and not on the positive cations. Following on these results, in the current paper we describe the time evolution of an excess electronic charge introduced in alkylammonium- and pyrrolidinium-based ionic liquids coupled with the bis(trifluoromethylsulfonyl)amide ([Tf2N–]) anion. We find that on a 50 fs time scale an initially delocalized excess electron localizes on a single [Tf2N–] anion which begins a fragmentation process. Low-energy transitions have a very different physical origin on the several femtoseconds time scale when compared to what occurs on the picosecond time scale. At time zero, these are intraband transitions of the excess electron. However after 40 fs when the excess electronic charge localizes on a single anion, these transitions disappear, and the spectrum is dominated by electron-transfer transitions between the fragments of the doubly charged breaking anion.
Details
- Title: Subtitle
- Dynamics of Excess Electronic Charge in Aliphatic Ionic Liquids Containing the Bis(trifluoromethylsulfonyl)amide Anion
- Creators
- Changhui XuAleksander DurumericHemant K KashyapJorge KohanoffClaudio J Margulis
- Resource Type
- Journal article
- Publication Details
- Journal of the American Chemical Society, Vol.135(46), pp.17528-17536
- Publisher
- American Chemical Society
- DOI
- 10.1021/ja409338z
- PMID
- 24156701
- ISSN
- 0002-7863
- eISSN
- 1520-5126
- Language
- English
- Date published
- 11/20/2013
- Academic Unit
- Chemistry
- Record Identifier
- 9983985867502771
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