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Challenge in Accurate Measurement of Fast Reversible Bimolecular Reaction Kyril M. Solntsev and Dan Huppert
 

Summary: Challenge in Accurate Measurement of Fast Reversible Bimolecular Reaction
Kyril M. Solntsev and Dan Huppert
School of Chemistry, Sackler Faculty of Exact Sciences, Tel-AViV UniVersity, Tel AViV 69978, Israel
Noam Agmon*
The Fritz Haber Research Center, Department of Physical Chemistry, The Hebrew UniVersity,
Jerusalem 91904, Israel
ReceiVed: December 22, 2000; In Final Form: March 28, 2001
Reversible bimolecular chemical reactions of the AB h 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.
1. Introduction
Chemical reactions occur over a vast range of time scales.1
Chemists routinely monitor reactions from femtoseconds (fs)
to hours. Historically, only slow chemical reactions could have
been monitored in the time domain, with samples regularly

  

Source: Agmon, Noam - Institute of Chemistry, Hebrew University of Jerusalem

 

Collections: Chemistry