Evidence for laser-induced formation of solvated electrons in room temperature ionic liquids.
The photolytic generation of solvated electrons was observed for the first time in two room temperature ionic liquids (RTILs), trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide (IL) and 1-butyl-1-methyl-pyrrolidinium bis(trifluoromethylsulfonyl)imide (IL). A 70 fs UV-pulse was used to excite the RTILs, while the transient response was monitored in the visible and near-infrared spectral regions. Immediately after excitation, a pulse duration limited rise of the induced absorption indicated the formation of solvated electrons suggesting the existence of pre-formed traps in RTILs. A broad transient absorption spectrum with a full width at half maximum of about 0.9 eV, typical for solvated electrons, was reconstructed from the transient profiles. Wavelength-independent relaxation dynamics at longer delay times suggest a lifetime of solvated electrons in the ns regime in agreement with results from pulse radiolysis studies. Adding 1,1-dimethylpyrrolidinium iodide to IL led to an increase of the UV absorbance and consequently, to an increase of the yield of solvated electrons. Furthermore, this solute is an efficient electron scavenger causing the transients to decay within about 40 ps.
Chandrasekhar
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Institut für Physikalische Chemie, Lehrstuhl für Molekulare Physikalische Chemie, Universität Karlsruhe (TH), Kaiserstr. 12, 76128, Karlsruhe, Germany.
Endres
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F
Unterreiner
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AN
D000042:Absorption; D003198:Computer Simulation; D004583:Electrons; D016166:Free Radical Scavengers / Q000737:chemistry; D007094:Imides / Q000737:chemistry; D007477:Ions / Q000737:chemistry*; D007834:Lasers; D008956:Models, Chemical; D010777:Photochemistry; D010782:Photolysis; D010880:Piperidines / Q000737:chemistry; D011759:Pyrrolidines / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet; D013696:Temperature; D014466:Ultraviolet Rays
D016166:Free Radical Scavengers; D007094:Imides; D007477:Ions; D010880:Piperidines; D011759:Pyrrolidines