UV photolysis of I3 - in solution - Multiple product channels detected by transient hyperspectral probing

Adva Baratz, Sanford Ruhman*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

16 Scopus citations

Abstract

Recombination of triiodide is followed in several polar liquids using femtosecond hyperspectral probing. Results reveal narrowing and blue shifting in product absorbance for tens of picoseconds coinciding with a delayed stage of geminate recombination. Global kinetic analysis suggests both can be assigned to a distinct fragment population other than free solvated diiodide, most likely caged [· I2 - ; · I] contact pairs. Interaction between the fragments is proposed to alter oscillator strengths and transition energies of the diiodide absorption bands, with the spectral evolution reflecting recombination of contact pairs to regenerate I3 -. Charge transfer between the caged fragments is proposed to be the step determining the rates of recombination explaining its delayed nature.

Original languageEnglish
Pages (from-to)211-217
Number of pages7
JournalChemical Physics Letters
Volume461
Issue number4-6
DOIs
StatePublished - 20 Aug 2008

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