Ultrafast mid-IR detection of the direct precursor to the presolvated electron following electron ejection from ferrocyanide

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. (C) 2000 Elsevier Science B.V. All rights reserved.