Na. Anderson et al., Ultrafast mid-IR detection of the direct precursor to the presolvated electron following electron ejection from ferrocyanide, CHEM P LETT, 329(5-6), 2000, pp. 386-392
Excitation of Fe(CN)(6)(4-) complex in D2O solution with a 267 nm ultrashor
t laser pulse results in rapid charge-transfer-to-solvent, and subsequent e
lectron hydration, Mid-IR transient absorption spectroscopy is used to inve
stigate the ejection and earliest steps in electron solvation. A broad, int
ense absorption signal is observed with instrument-response-limited rise an
d 170 +/- 20 fs single exponential decay at all probe wavelengths studied,
stretching from similar to3 to 7 mum. No significant solvent isotope depend
ence in the time-evolution was seen. The spectral and temporal characterist
ics of the mid-IR signal provide strong evidence that it arises from a step
in solvation immediately preceding formation of the presolvated electron.
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