Excited-state proton transfer in methanol-doped ice in the presence of KF

Anna Uritski, Dan Huppert*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

7 Scopus citations

Abstract

Steady-state and time-resolved emission techniques were employed to study the photoprotolytic cycle of an excited photoacid in ice in the presence of a low concentration of a weak base-like F-. In previous studies we found that the photoprotolytic cycle in methanol-doped ice (1% mol fraction) is too slow to be observed at temperatures below 190 K. In this study we found that at temperatures below 240 K an additional proton-transfer process occurs in ice doped with 10 mM KF. We attributed this reaction to the creation of a mobile L-defect by F- ions. We used a diffusion-assisted reaction model, based on the Debye-Smoluchowski equation, to account for the direct reaction of the L-defect with the excited photoacid at temperatures below T < 240 K. Below 160 K the spectroscopic properties as well as the photoprotolytic cycle change dramatically. We propose that below 160 K the sample enters a new phase. The excited-state proton-transfer (ESPT) process was observed and followed down to a liquid nitrogen temperature of ∼78 K. In the low-temperature phase the ESPT rate is almost twice as much as at 180 K and the temperature dependence of the rate is very small. The kinetic isotope effect of the ESPT at the low-temperature phase is small of about 1.3.

Original languageEnglish
Pages (from-to)4415-4425
Number of pages11
JournalJournal of Physical Chemistry A
Volume112
Issue number19
DOIs
StatePublished - 15 May 2008

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