title: Photodetachment and electron reactivity in 1-methyl-1-butyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide.
abstract: The transient absorption spectrum in the range 500 nm-1000 nm was measured with ultrafast time resolution on a flowing neat, aliphatic, room-temperature ionic liquid following anion photodetachment. In this region the spectrum was shown to be a combination of absorption from the electron and the hole. Spectrally-resolved electron quenching determined a bimodal shape for the hole spectrum in agreement with recent computational predictions on a smaller aliphatic ionic liquid [Margulis et al., J. Am. Chem. Soc. 133, 20186 (2011)]. For time delays beyond 15 ps, spectral evolution qualitatively agrees with recent radiolysis experiments [Wishart et al., Faraday Discuss. 154, 353 (2012)]. However, the shape of the spectrum is different, reflecting the contrast in ionization energy between the two methods. Previously unobserved reactivity of the electron was found with a time constant of 300 fs. The results demonstrate solvent control of the rate coefficient for reaction between the electron and proton, with a rapid decline in the rate within the first picosecond.
authors: Department of Chemistry, University of Minnesota, 207 Pleasant St. SE, Minneapolis, Minnesota 55455, USA.
authors: Francesc
authors: F
authors: Molins i Domenech
authors: Benjamin
authors: B
authors: FitzPatrick
authors: Andrew T
authors: AT
authors: Healy
authors: David A
authors: DA
authors: Blank