Challenge in accurate measurement of fast reversible bimolecular reaction

Kyril M. Solntsev, Dan Huppert, Noam Agmon

Research output: Contribution to journalArticlepeer-review

Abstract

Reversible bimolecular chemical reactions of the AB ⇌ A + B type were predicted theoretically to deviate from exponential kinetics, obeying convolution kinetics at intermediate times and ultimately approaching equilibrium as a power law, t-3/2, with a concentration-dependent amplitude. By careful application of time-resolved fluorescence methods, we verify these predictions for excited-state proton transfer from 2-naphthol-6,8-disulfonate to acidified water. The variation of the asymptotic amplitude with concentration is due predominantly to screening of the proton-anion Coulomb potential, and this masks the many-body effects on reversible binding itself. Better signal-to-noise in the long-time tails is required for clearly establishing the asymptotic behavior.

Original languageEnglish
Pages (from-to)5868-5876
Number of pages9
JournalJournal of Physical Chemistry A
Volume105
Issue number24
DOIs
StatePublished - 21 Jun 2001

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